Composite dispersion and process for producing the same

ABSTRACT

A resin comprises a resin containing a vulcanization-activating agent, or crosslinkable group-containing resin (e.g., a resin having an unsaturated bond). Moreover, a composite dispersion may be formed by a combination of a specific resin and rubber [e.g., (a) a combination of a resin, and an unvulcanized rubber containing a vulcanizing agent and a vulcanization-activating agent at a specific ratio; (b) a combination of a polyamide-series resin, and an unvulcanized rubber containing a vulcanizing agent and a polyalkenylene at a specific ratio; (c) a combination of a resin and a silicone-series unvulcanized rubber; and (d) a combination of a polyphenylene ether-series resin containing a polyalkenylene, and an unvulcanized rubber containing a sulfur or sulfur-containing organic compound as a vulcanizing agent]. The present invention provides a composite dispersion which comprises a continuous phase comprising a resin, and a dispersed phase being firmly bonded to the continuous phase and comprising a vulcanized rubber in a wide range of a combination of the resin and the rubber.

TECHNICAL FIELD

The present invention relates to a composite dispersion (or compositedispersion material) comprising a resin and a rubber, and being usefulfor a mechanical part or a machine element, an automobile part and soon, and relates to a process for producing the same.

BACKGROUND ART

With request for higher qualities of polymeric materials, materialshaving multiple properties, in some cases, materials having combinedproperties opposite to each other have been required. In particular, inthe field of industrial polymeric materials, materials having combinedproperties (e.g., high rigidity and impact resistance, flexibility andchemical resistance, or abrasion resistance and oil resistance) havebeen demanded, and the development of compositions obtained by combiningvarious resins with vulcanized rubbers (or rubbers) has been desired.

However, materials having different properties are not usuallycompatible with each other, so that simple mixing of both the materialsonly obtains a mixture in which one component is inhomogeneouslydispersed in the other. Therefore, it is difficult to give a compositionhaving such a new property as to be a combination of properties of boththe materials. If anything, such a mixture often entails deteriorationin important properties as an industrial material (e.g., breakingelongation (or elongation at break), cold resistance), and in many casesit cannot become practicable technique. These defects are solved byfirmly bonding the interfaces of both the components to each other inmixing of the both to give a similar effect in as the case the bothbeing substantially compatible with each other at the interfaces.

To date, many methods for obtaining a composite of a resin member bondedto a rubber member have been proposed. In mixing a resin and a rubber,it is considered that utilization of these composite techniques ensure anew composition (composite dispersion) in which one component isdispersed in the other component uniformly and both the interfaces areenough bonded to express both properties in combination.

As a process for obtaining a composite of a rubber member bonded to aresin member, for example, a process which comprises bonding both themembers by an adhesive has been known. However, in the case obtaining acomposite by utilizing an adhesive, it is necessary to interpose theadhesive between the resin and the rubber intensively. However, inmixing of these three components, it is difficult to interpose theadhesive only in the interface of the rubber and the resin, andthroughout the interface.

Moreover, a method bonding a resin-molded member to a rubber-moldedmember directly has been proposed. For example, Japanese PatentApplication Laid-Open No. 25682/1975 (JP-50-25682A) discloses a processfor producing a composite, which comprises rubbing a thermoplasticplastic and a vulcanized rubber compatible with the thermoplasticplastic with contacting each other to melt or fuse the surface of theplastic, and solidifying the resultant mixture with contacting thethermoplastic resin component and the vulcanized rubber component.However, in the process, it is difficult to produce an object composite.

Japanese Patent Application Laid-Open No. 124803/1997 (JP-9-124803A)discloses a process for producing a composite member, which comprisesheating an acrylonitrile-containing thermoplastic resin (e.g., AS resin,ABS resin, etc.) with an acrylonitrile-containing rubber with intimatelycontacting each other through the use of compatibility between thethermoplastic resin and the rubber. However, this process markedlyrestricts species of resins and rubbers because both of them shouldcontain acrylonitrile, and therefore the practical applications are muchlimited.

Japanese Patent Application Laid-Open No. 156288/1996 (JP-8-156288A)discloses a process for producing a composite member, which comprisesvulcanizing an epoxy group-containing resin composition whichestablishes contact with an elastic rubber having a vulcanized carboxylgroup or an acid anhydride group, and bonding the contact surfacebetween the resin composition and the rubber through the use of achemical reaction of an epoxy group with a carboxyl group. However,since this process uses the chemical reaction of the epoxy group withthe carboxyl group, species of the resin and the rubber are markedlylimited, and it is difficult to obtain composites widely.

Japanese Patent Application Laid-Open No. 150439/1990 (JP-2-150439A),Japanese Patent Application Laid-Open No. 133631/1991 (JP-3-133631A) andJapanese Patent Application Laid-Open No. 138114/1991 (JP-3-138114A)propose a process for producing a composite, which comprises vulcanizinga polyamide-series resin and a rubber component in the presence of avulcanizing system, wherein the rubber component comprises a carboxylgroup- or an acid anhydride group-containing rubber, a peroxide, avulcanization-activating agent (e.g., ethylene glycol dimethacrylate,triallyl isocyanurate, etc.), and an alkoxysilane compound. In thesedocuments, a polyamide-series resin containing the larger number of aterminal amino group than that of a terminal carboxyl group is mostlyused as an aliphatic polyamide-series resin. That is, this processutilizes a reaction of an amino group with a carboxyl group or an acidanhydride group. Therefore, the species of resins and that of rubbersare markedly restricted, and it is difficult to obtain a resin-rubbercomposite in a wide range of the resin and the rubber.

Japanese Patent Application Laid-Open No. 11013/1995 (JP-7-11013A)discloses a process for producing a composite member of a vulcanizedrubber and a polyamide molded article, by bringing a polyamide moldedarticle into contact with a rubber compound containing a rubber, aperoxide vulcanizing agent and a silane compound and by vulcanizingthem.

However, the process does not only require a silane compound but alsorestricts the resin to a polyamide-series resin, so that the processalso has no versatility.

On the other hand, Japanese Patent Application Laid-Open No. 30221/2002(JP-2002-30221A) discloses a thermoplastic resin composition in which avulcanized rubber (A) is dispersed in the form of particle in acontinuous phase of a thermoplastic resin (B), wherein the rubber (A)and the thermoplastic resin (B) include combinations in which a resinmolded article and a rubber molded element comprising the rubber (A) arecapable of adhering at such a degree of an adhesive strength that acohesive failure occurs in a peel test, when the rubber (A) isvulcanized with bringing the resin molded article comprising thethermoplastic resin (B) into contact with the unvulcanized rubber (A)under pressure and heating.

This literature describes, as concrete combinations of a resin and arubber in which a cohesive failure occurs, (1) a combination of at leastone rubber selected from the group consisting of SBR, NR, EPDM, anacid-modified ethylene-propylene rubber and an ethylene-acrylicacid-acrylate copolymer rubber, and a polyphenylene ether (PPE) or acomposition thereof; and (2) a combination of at least one rubberselected from the group consisting of an acid-modifiedethylene-propylene rubber, an acid-modified nitrile rubber and afluorine-containing rubber, and a thermoplastic resin having an aminogroup. Further, the reference describes that an organic peroxide is usedas a rubber-vulcanizing agent in many cases, and the PPE composition maycomprise 100 parts by weight of the PPE, 0 to 30 parts by weight of apolyalkenylene, and 0 to 30 parts by weight of a styrenic rubber, in thecombination (1) of the PPE or the composition thereof. Moreover, it ismentioned in the literature that about 0.1 to 5 parts by weight of avulcanization accelerator (e.g., a benzothiazole compound,triallylisocyanurate, m-phenylenebismaleimide, trimethylolpropanetri(meth)acrylate), or about 0.5 to 12 parts by weight of apolyalkenylene (e.g., a polyoctenylene) as a processing synergist isadded to 100 parts by weight of the rubber.

However, in a method mentioned in the literature, it is difficult tofind a combination of a resin and a rubber with a cohesive failure, andthe combination of the resin and the rubber is significantly restricted.Moreover, even when such a combination is selected, an adhesive strengthbetween a continuous phase and a dispersed phase is not enough in manycases.

It is therefore an object of the present invention to provide acomposite dispersion (or a composited dispersion) which comprises acontinuous phase comprising a resin, and a dispersed phase being bondedto the continuous phase and comprising a vulcanized rubber in a widerange of combination of the resin and the rubber, and a process forproducing the same.

It is another object of the present invention to provide a process forproducing a composite dispersion, by a convenient process, whichcomprises a resin phase and a vulcanized rubber phase being firmlybonded to the resin phase.

It is still another object of the present invention to provide acomposite dispersion capable of imparting a rubber property to a resinmatrix effectively, and a process for producing the same.

It is a further object of the present invention to provide a moldedarticle formed from a composite dispersion which comprises a resin phaseand a vulcanized rubber phase being firmly bonded to the resin phase.

DISCLOSURE OF THE INVENTION

The inventors of the present invention made intensive studies to achievethe above objects and finally found that, in a composite dispersionformed by bonding a resin phase to a rubber phase, (1) use of a resincontaining a vulcanization accelerator or a crosslinkable resin, or (2)combination use of a specific resin and a rubber insures that the resinphase is directly bonded to the vulcanized phase certainly and firmly.The present invention has been accomplished based on the above findings.

That is, the composite dispersion (1) of the present invention comprisesa continuous phase comprising a resin, and a dispersed phase beingdirectly bonded to the continuous phase and comprising a vulcanizedrubber formed by vulcanizing an unvulcanized rubber, wherein thecontinuous phase comprises a resin containing a vulcanization-activatingagent, or a crosslinkable group-containing resin. Incidentally, the term“directly bonded” means that “a resin phase is bonded to a vulcanizedrubber phase without an adhesive, and mechanical peeling of the bothsheet-like phases progresses along with a cohesive failure of the rubberphase”.

The crosslinkable group-containing resin may be, for example, athermoplastic resin having an unsaturated bond (e.g., a thermoplasticresin having an unsaturated bond in a proportion of about 0.01 to 6.6mol relative to 1 kg of the thermoplastic resin). The thermoplasticresin having an unsaturated bond may be (i) a resin produced by areaction of a polymerizable compound having a reactive group (A) and anunsaturated bond with a thermoplastic resin having a reactive group (B)which is reactive to the reactive group (A), or (ii) a thermoplasticresin into which an unsaturated bond is introduced by copolymerizationor copolycondensation.

The resin may comprise at least one member selected from the groupconsisting of a polyamide-series resin (e.g., an aliphaticpolyamide-series resin), a polyester-series resin (e.g., an aromaticpolyester-series resin), a poly(thio)ether-series resin (e.g., apolyphenylene ether-series resin, and a polysulfide-series resin), apolycarbonate-series resin, a polyimide-series resin, apolysulfone-series resin, a polyurethane-series resin, apolyolefin-series resin, a halogen-containing resin, a styrenic resin, a(meth)acrylic resin, and a thermoplastic elastomer; or a resin having atleast two atoms on the average per molecule, and each of atoms isselected from a hydrogen atom and/or a sulfur atom and has an orbitalinteraction energy coefficient S of not less than 0.006, wherein theorbital interaction energy coefficient S is represented by the followingformula (1):S=(C _(HOMO,n))² /|E _(c) −E _(HOMO,n)|+(C _(LUMO,n))² /|E _(c) −E_(LUMO,n)|  (1)

in the formula, each of E_(c), C_(HOMO,n), E_(HOMO,n), C_(LUMO,n), andE_(LUMO,n) represents a value calculated by a semiempirical molecularorbital method MOPACPM3, E_(C) representing an orbital energy (eV) of aradical of a radical-generating agent, C_(HOMO,n) representing amolecular-orbital coefficient of the highest occupied molecular orbital(HOMO) of an n-th hydrogen atom and/or sulfur atom constituting a basicunit of the resin, E_(HOMO,n) representing an orbital energy (eV) of theHOMO, C_(LUMO,n) representing a molecular-orbital coefficient of thelowest unoccupied molecular orbital (LUMO) of the n-th hydrogen atomand/or sulfur atom constituting the basic unit of the resin, andE_(LUMO,n) representing an orbital energy (eV) of the LUMO.

In the composite dispersion (1), the vulcanized rubber may comprise adiene-series rubber, an olefinic rubber, an acrylic rubber, afluorine-containing rubber, a silicone-series rubber, a urethane-seriesrubber, and others. At least the unvulcanized rubber may contain avulcanizing agent (e.g., a radical-generating agent such as an organicperoxide, an azo compound and a sulfur-containing organic compound, anda sulfur). The proportion of the vulcanizing agent may be about 0.1 to10 parts by weight relative to 100 parts by weight of the unvulcanizedrubber. Moreover, the vulcanization-activating agent may comprise atleast one member selected from the group consisting of an organiccompound having at least two polymerizable unsaturated bonds permolecule, and a maleimide-series compound. The proportion of thevulcanization-activating agent may be about 0.1 to 10 parts by weightrelative to 100 parts by weight of the resin. Further, at least onecomponent selected from the group consisting of the resin and theunvulcanized rubber may contain a polyalkenylene. The proportion of thepolyalkenylene may be about 1 to 30 parts by weight relative to 100parts by weight of the resin or the unvulcanized rubber.

In the composite dispersion (2), a combination of the resin and/or theunvulcanized rubber may be any one of the following combinations (a) to(d). Incidentally, in these combinations, the resin may have at leasttwo atoms on the average per molecule, and each of the atoms is selectedfrom a hydrogen atom and/or a sulfur atom and has the orbitalinteraction energy coefficient S of not less than 0.006. Moreover, theunvulcanized rubber may contain a vulcanization-activating agent or apolyalkenylene.

-   -   (a) a combination of a resin, and an unvulcanized rubber        containing a vulcanizing agent and a vulcanization-activating        agent, wherein the weight ratio of the vulcanizing agent        relative to the vulcanization-activating agent [the former/the        latter] is 2/98 to 70/30;    -   (b) a combination of a polyamide-series resin, and an        unvulcanized rubber containing a vulcanizing agent and a        polyalkenylene, wherein the weight ratio of the vulcanizing        agent relative to the polyalkenylene [the former/the latter] is        2/98 to 45/55;    -   (c) a combination of a resin and a silicone-series unvulcanized        rubber; and    -   (d) a combination of a polyphenylene ether-series resin        containing a polyalkenylene, and an unvulcanized rubber        containing a sulfur or a sulfur-containing organic compound as a        vulcanizing agent.

In the composite dispersion of the present invention, the resin and/orthe unvulcanized rubber may have a molecular weight of not more than1000, and may comprise at least one member selected from the groupconsisting of the following compounds: a compound having two hydrogenatoms on the average per molecule, each atom having the orbitalinteraction energy coefficient S of not less than 0.006; a compoundhaving not less than one group selected from the group consisting of acarboxyl group, an acid anhydride group and an isocyanate group permolecule; and a silane coupling agent. Moreover, in the compositedispersion of the present invention, the continuous phase and thedispersed phase may form an islands-in-an ocean structure. The weightratio of the continuous phase relative to the dispersed phase may beabout 25/75 to 98/2.

The present invention includes a process for producing the compositedispersion, which comprises kneading a resin and an unvulcanized rubberto give the composite dispersion, and a shaped article which is formedfrom the composite dispersion.

Incidentally, in the present invention, the resin includes a graftcopolymer containing a rubber component (for example, HIPS, ABS resin).

DETAILED DESCRIPTION OF THE INVENTION

The composite dispersion of the present invention comprises a continuousphase comprising a resin (sometimes simply referred to as a resinphase), and a dispersed phase being bonded to the continuous phase andcomprising a vulcanized rubber obtained by vulcanizing an unvulcanizedrubber (sometimes simply referred to as a rubber phase). In oneembodiment of the present invention, a resin is firmly bonded to arubber by using a resin containing a vulcanization-activating agent or acrosslinkable group-containing resin as the resin in the compositedispersion. Moreover, in other embodiment of the present invention, thecomposite dispersion comprises a specific resin and a rubber incombination.

[Resin]

As the resin constituting the continues phase, a thermoplastic resin orthe like may be used.

The thermoplastic resin includes, for example, a condensation-seriesthermoplastic resin [e.g., a polyamide-series resin, a polyester-seriesresin, a polyurethane-series resin, a poly(thio)ether-series resin(e.g., a polyacetal-series resin, a polyphenylene ether-series resin, apolysulfide-series resin, a polyether ketone-series resin), apolycarbonate-series resin, a polyimide-series resin, apolysulfone-series resin, or a polyurethane-series resin]; a vinylpolymerizable thermoplastic resin [e.g., a polyolefinic resin, a(meth)acrylic resin, a styrenic resin, a halogen-containing resin, avinyl-series resin (e.g., a polyvinyl acetate, a polyvinyl alcohol)]; athermoplastic elastomer; and the like.

These resins may be used singly or in combination. When two or morespecies of the resins are used, a resin composition may form a compositeresin composition such as a polymer alloy.

(Crosslinkable Group-Containing Resin)

The crosslinkable group-containing resin (or a resin having acrosslinkable group) (hereinafter, sometimes referred to as acrosslinkable resin) includes, for example, a thermoplastic resin havingan unsaturated bond (polymerizable or crosslinkable unsaturated bond).With the use of such a crosslinkable resin, since a crosslinkingreaction also progresses at an interface between a rubber component anda resin component in vulcanization of the rubber component, even if arubber component in a wide extent is selected as the rubber component, aresin phase can firmly bond to a rubber phase (or a vulcanized rubberphase).

In a thermoplastic resin having an unsaturated bond, the unsaturatedbond is not particularly restricted to a specific bond as far as theunsaturated bond can be activated by a vulcanizing agent such as aradical-generating agent, there may be exemplified various bonds(particularly polymerizable unsaturated bonds) showing crosslinkableability or polymerizable ability by imparting of heat or light. Such anunsaturated bond or a unit having an unsaturated bond may bond to athermoplastic resin through a connection group [e.g., an ester bond(—OC(═O)—, —C(═O)O—), an amide bond (—NHCO—, —CONH—), an imino bond(—NH—), aurethane bond (—NHC(═O)O—), a urea bond, a biuret bond].Further, the unsaturated bond or the unit may be located either in aterminal of the resin (terminal of a main chain) and/or in a side chainof the resin, or in a main chain of the resin. Furthermore, theunsaturated bond or the unit may be located in a terminal and/or sidechain of the resin, in a main chain of the resin, or both.

As the group having an unsaturated bond, there may be exemplified, forexample, a C₂₋₆alkenyl group such as vinyl group, 1-propenyl group,isopropenyl group, 1-butenyl group, allyl group, 2-methyl-2-propenylgroup, or 2-butenyl group; a C₂₋₆alkenyl-C₆₋₂₀aryl group such as4-vinylphenyl group, or 4-isopropenylphenyl group; aC₆₋₂₀aryl-C₂₋₆alkenyl group such as styryl group; a C₂₋₆ alkynyl groupsuch as ethynyl group, 1-propynyl group, 1-butynyl group, propargylgroup, 2-butynyl group, or 1-methyl-2-propynyl group; a vinylene groupwhich may have a substituent, for example, vinylene group, a mono- ordi-C₁₋₆alkylvinylene group such as methylvinylene group, ethylvinylenegroup or 1,2-dimethylvinylene group, and a halovinylene group such as achlorovinylene group; a vinylidene group; an ethynylene group; and thelike.

Concrete embodiments of the thermoplastic resin having an unsaturatedbond can be illustrated by the following embodiments such as (i) to(iii):

-   -   (i) a resin produced by a reaction of a polymerizable compound        having a reactive group (A) and an unsaturated bond with a        thermoplastic resin having a reactive group. (B) which is        reactive to the reactive group (A),    -   (ii) a thermoplastic resin into which an unsaturated bond is        introduced by copolymerization or copolycondensation, and    -   (iii) a thermoplastic resin into which an unsaturated bond is        introduced by various organic reactions (e.g., introduction of a        vinyl group by Reppe reaction using acetylene, introduction of        an unsaturated bond using an organic metal reagent such as vinyl        lithium, introduction of an unsaturated bond by coupling        reaction).

Among these resins, the preferred unsaturated bond-containing resin isthe foregoing resin (i) or (ii).

In the resin (i), an unsaturated bond can be introduced into a resin bya reaction of a polymerizable compound having at least one reactivegroup (A) and at least one unsaturated bond, with a resin having areactive group (B) which is reactive to the reactive group (A) in thepolymerizable compound.

As such a representative reactive group (A) in a polymerizable compound,there may be mentioned, for example, (A1) hydroxyl group, (A2) carboxylgroup or acid anhydride group thereof, (A3) amino group, (A4) epoxygroup, (A5) isocyanate group, and the like. As the combination of areactive group (A) in a polymerizable compound with a reactive group (B)in a resin, the following combinations can be exemplified. Incidentally,words in the parentheses show a bond form (type or mode) between thereactive group (A) and the reactive group (B).

-   -   (A1) hydroxyl group:    -   (B) carboxyl group or acid anhydride group thereof (ester bond),        isocyanate group (ester bond)    -   (A2) carboxyl group or acid anhydride group thereof:    -   (B) hydroxyl group (ester bond), amino group (amide bond), epoxy        group (ester bond), isocyanate group (amide bond)    -   (A3) amino group:    -   (B) carboxyl group or acid anhydride group thereof (amide bond),        epoxy group (imino bond), isocyanate group (amide bond)    -   (A4) epoxy group:    -   (B) carboxyl group or acid anhydride group thereof (ester bond),        amino group (imino bond)    -   (A5) isocyanate group:    -   (B) hydroxyl group (ester bond), carboxyl group or acid        anhydride group thereof (amide bond), amino group (amide bond)

The polymerizable compound can be exemplified by a hydroxylgroup-containing compound [e.g., a C₃₋₆alkenol such as allylalcohol,2-buten-1-ol or 3-buten-2-ol; a C₃₋₆alkynol such as propargyl alcohol; aC₂₋₆alkylene glycol mono(meth)acrylate such as2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, orbutanediol mono(meth)acrylate; a polyoxyC₂₋₆alkylene glycolmono(meth)acrylate such as diethylene glycol mono(meth)acrylate; aC₂₋₆alkenylphenol such as 4-hydroxystyrene or 4-hydroxy-α-methylstyrene;dihydroxystyrene; vinylnaphthol], a compound containing a carboxyl groupor an acid anhydride group thereof [e.g., a C₃₋₆alkene-carboxylic acidsuch as (meth)acrylic acid, crotonic acid or 3-butene acid; aC₄₋₈alkene-dicarboxylic acid or an anhydride thereof such as itaconicacid, maleic acid or maleic anhydride; an unsaturated aromaticcarboxylic acid such as vinyl benzoic acid; cinnamic acid], a compoundcontaining an amino group (e.g., a C₃₋₆ alkenylamine such as allylamine,4-aminostyrene, diaminostyrene), a compound containing an epoxy group(e.g., allyl glycidyl ether, glycidyl(meth)acrylate), a compoundcontaining an isocyanate group (e.g., vinylisocyanate) and the like.

Incidentally, in the resin (i), the resin may be reformed or modified bybeing introduced a reactive group (B). As the method for introducing thereactive group (B) into the resin, there may be utilized: (i-1) a methodcopolymerizing a monomer having a reactive group (B) (such as theabove-exemplified polymerizable compound) with a resin material (or amonomer or oligomer, the resin raw materials) in the resin production,and (i-2) various organic reactions such as an oxidative reaction forintroduction of a carboxyl group, a halogenation method, a graft methodof a polymerizable monomer. Incidentally, in the vinyl polymerizableresins, the reactive group (B) is usually introduced (into the resin)with the use of a monomer having the reactive group (B) as acopolymerizable component, and in any resins including the vinylpolymerizable resins, the reactive group (B) can be easily introduced bygraft reaction of the polymerizable compound having the reactive group.

In the resin (ii), as a method for introducing an unsaturated bond,there may be mentioned, for example, a method which comprisescopolycondensing (or copolymerizing) a compound having a polyfunctionalunsaturated bond as a part of a reactive component (comonomer) [e.g., anunsaturated polycarboxylic acid (or an unsaturated polybasic carboxylicacid) such as an aliphatic unsaturated dicarboxylic acid (e.g., a C₄₋₁₀aliphatic unsaturated dicarboxylic acid such as maleic acid, maleicanhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconicacid, citraconic anhydride, or methaconic acid); an unsaturatedpolyhydric alcohol such as an aliphatic unsaturated diol (e.g., a C₄₋₁₀aliphatic unsaturated diol such as 2-buten-1,4-diol)] in a production ofa condensation-series resin (such as a polyamide-series resin, apolyester-series resin). Moreover, in an addition polymerization-seriesresin (such as an olefinic resin), there may be exemplified a methodwhich comprises copolymerizing a monomer having a conjugated unsaturatedbond (e.g., a conjugated C₄₋₁₀ alkadiene which may have a substituent,such as 1,3-butadiene, 2-methyl-1,3-butadiene,2,3-dimethyl-1,3-butadiene, or chloroprene) as a part of a reactivecomponent (comonomer).

The resin(s) having an unsaturated bond may be used singly or incombination. Moreover, the resin having an unsaturated bond may containa resin (a) which is free from an unsaturated bond. The resin (a) is notparticularly limited, and includes various thermoplastic resins [forexample, a thermoplastic resin as described below (e.g., apolyamide-series resin, and a polyester-series resin)].

The proportion of the resin (a) may for example be about 10 to 3000parts by weight, preferably about 15 to 2000 parts by weight, and morepreferably about 30 to 500 parts by weight (e.g., about 50 to 300 partsby weight) relative to 100 parts by weight of the resin having anunsaturated bond.

The number of the unsaturated bond is, for example, not less than 0.1(e.g., about 0.1 to 1000) on the average per molecule of the resin,preferably not less than 1 (e.g., about 1 to 100) on the average, andmore preferably not less than 2 (e.g., about 2 to 50) on the average.Moreover, the concentration of the unsaturated bond is, for example,about 0.001 to 6.6 mole relative to 1kg of resin, preferably about 0.01to 4 mole, and more preferably about 0.02 to 2 mole.

(Resin having an Active Atom)

The resin to be used in the present invention may have an atom showinghigh activity to a radical-generating agent (hereinafter, referred to asan active atom). Such an active atom can increase an activity of a resinto a vulcanizing agent in the case using a radical-generating agent as avulcanizing agent, and insures improvement in adhesive strength betweenthe resin and the rubber.

Concretely, the resin may be selected depending on the species of theradical-generating agent, and may for example have an active atom (e.g.,an active hydrogen atom, an active sulfur atom) having an orbitalinteraction energy coefficient S represented by the following formula(1) of not less than a given value (e.g., 0.006, and preferably 0.008).The preferred value of the orbital interaction energy coefficient S ofthe active atom is about 0.006 to 0.06, and preferably about 0.007 to0.05 (in particular about 0.01 to 0.045). The number of the active atomdepends on a bonding position or site of a functional group having theactive atom (e.g., an end or terminal, a branched chain, or a mainchain), and the number of the active atom per molecule of the resin is,for example, not less than 2 (about 2 to 10000) on the average,preferably not less than 2.5 (about 2.5 to 5000) on the average, andmore preferably not less than 3 (about 3 to 1000) on the average. Thenumber of the active atom per molecule of the resin is usually about 2to 100 (preferably about 2.5 to 50, more preferably about 3 to 25, andparticularly about 3 to 20).S=(C _(HOMO,n))² /|E _(c) −E _(HOMO,n)|+(C _(LUMO,n))² /|E _(c) −E_(LUMO,n)|  (1)

wherein each of the factors, E_(c), C_(HOMO,n), E_(HOMO,n), C_(LUMO,n),and E_(LUMO,n) representing a value calculated by the semiempiricalmolecular orbital method MOPACPM3, E_(c) representing an orbital energy(eV) of a radical of a radical-generating agent; C_(HOMO,n) representinga molecular-orbital coefficient of the highest occupied molecularorbital (HOMO) of an n-th hydrogen atom and/or sulfur atom constitutinga basic (or constitutive) unit of the resin; E_(HOMO,n) representing anorbital energy (eV) of the HOMO; C_(LUMO,n) representing amolecular-orbital coefficient of the lowest unoccupied molecular orbital(LUMO) of the n-th hydrogen atom and/or sulfur atom constituting thebasic unit of the resin; and E_(LUMO,n) representing an orbital energy(eV) of the LUMO.

MOPACPM3 represented by the formula (1) is one of molecular orbital (MO)methods. The molecular orbital method is one of approximations fordiscussing an electron condition or state in a molecular, and isclassified into three main methods; an empirical method such as Huckel'srule, a semiempirical method enhancing an approximation of the Huckel'srule, and an nonempirical method determining strictly a molecularorbital function by only calculation. In recent years, with developing acomputer system, the semiempirical method and the nonempirical methodare main methods. The molecular orbital method is a most convinciblemethod correlating a molecular structure and chemical reactivitythereof. For example, when searching the term “molecular orbital method”as a keyword in JST Online Information System (JOIS), about 53000 of aregistered number can be found (term: 1980 to 2000 May). The MOPACPM3 isthe core of NDDO (Neglect of Diatomic Differential Overlap) method whichis one of the semiempirical methods.

The MOPACPM3 is used for mainly studying a reaction of an organiccompound, and is explained in many literatures and publications [e.g.,“Molecular orbital method MOPAC guidebook” (Tsuneo Hirano, KazutoshiTanabe; Kalbundo, 1991), “Introduction to Quantum Chemistry, 3rd revisededition” (Teijiro Yonezawa et al., Kagaku Dojin, 1983), “CalculationChemistry giudebook” (translated by Eiji Osawa et al., written by TimClark, Maruzen, 1985)].

A basic unit (or constitutive unit) in the formula (1) means a modelingmolecular structure comprising a polymer terminal and about 1 to 3repeating unit (s). That is, it is difficult to calculate a molecularorbital for a polymer compound itself by MOPACPM3, since the polymercompound has too much numbers of atoms per molecule. Therefore, acalculation may be carried out for a modeling molecular structure (aconstitutive unit or basic unit) comprising a polymer terminal and about2 to 3 repeating units. For example, a molecular structure (repeatingunit) of a polybutylene terephthalate (PBT) is generally represented bya chemical formula “—(CH₂—CH₂—CH₂—CH₂—O—C(═O)—C₆H₄—C(═O)—O)_(n)—”, andthe calculation of a molecular orbital in the formula (1) may beconducted for “HO—CH₂—CH₂—CH₂—CH₂—O—C(═O)—C₆H₄—C(═O)—OH” as a basicunit.

The orbital interaction energy coefficient S represented by the formula(1) may be referred to as a reactive index, and is defined and explainedin various publications. When a chemical reactivity is discussed, theorbital interaction energy coefficient S is used as a parameter for thechemical reactivity in general. For example, “Introduction of Frontierorbital theory” (p. 72, Shinichi Yamabe, Satoshi Inagaki, KodanshaScientific, 1989) describes that an orbital interaction energycoefficient S indicates a concept “Regarding to an interaction betweentwo orbits, (a) a smaller energy difference between two orbits and (b) alarger overlap between two orbits make the interaction stronger”. Theformula (1) is based upon an idea of super delocalizability (Sr)published in 1954 by late Dr. Fukui given a Nobel prize (see “To use amolecular orbital method”, p. 71, Minoru Imoto, Kagaku Dojin, 1986), aformula similar to the formula (1) is derived from the concept of Sr onvarious publications and literatures.

Hereupon, it is important that the molecular orbital method is alreadywidely known for discussion of a molecular structure and chemicalreactivity thereof. Therefore, an orbital interaction energy coefficientS (1/eV) defined by the formula (1) does not represent a mere conceptualvalue, and represents a value meaning a parameter or properties of amaterial (e.g., a molecular weight, a functional group) fordetermination of the material.

Incidentally, the radical orbital energy E_(c) (eV) of aradical-generating agent is preferably calculated based on a radicalmolecular structure with the use of MOPACPM3, and a predetermined valuebased on a species of the radical-generating agent may be used forconvenience. For example, the E_(c) value of the radical-generatingagent may be −8 eV for an organic peroxide, −5 eV for an azo compound,and −6 eV for a sulfur-containing organic compound excluding a sulfur.

As the hydrogen atom having not less than a predetermined value (e.g.,0.006) of an orbital interaction energy coefficient S (an activehydrogen atom) in the case where the radical-generating agent comprisesan organic peroxide, there may be mentioned, for example, a hydrogenatom constituting an amino group (—NH₂) (e.g., a terminal amino group),an imino group (—NH—) (e.g., a main-chain or terminal imino group, —NH—of an amide bond), a methyl group (—CH₃), a methylene group (—CH₂—) (amethylene group in a main chain, or terminal methylene group), or amethylidyne group (—CH═) (a main-chain or terminal methylidyne group).

As the sulfur atom having not less than a predetermined value (e.g.,0.006) of an orbital interaction energy coefficient S (an active sulfuratom), in the case where the radical-generating agent comprises anorganic peroxide, there may be mentioned, for example, a sulfur atomconstituting a thio group (—S—), a mercapto group (—SH), an alkylthiogroup (e.g., a C₁₋₄alkylthio group such as a methylthio group, or anethylthio group), or a sulfinyl group (—SO—).

The methyl group includes, for example, a methyl group bonding to analkylene chain, a cycloalkylene chain, or an aromatic ring; a methylgroup bonding to an oxygen atom (e.g., a methyl group in a methoxygroup). The methylene group may include, for example, a methylene groupof a linear or branched alkylene group forming a main chain or sidechain, a methylene group of a (poly)oxyalkylene unit such as a(poly)oxymethylene unit or a (poly)oxyethylene unit, and a methylenegroup adjacent to a nitrogen atom of an amino group or an imino group.The methylidyne group includes, for example, an α-positioned methylidynegroup adjacent to an amino group or an imino group, such as amethylidyne group α-positioned to an amino group in an aminocycloalkylgroup.

It is sufficient that a resin having an active atom has plural (e.g.,not less than 2 on average) active atoms per molecule. That is, usuallythe resin is not constituted by a single molecule, and comprises amixture of numerous molecules being somewhat different in a structureand a chain length. Therefore, all molecules of the resin are notrequired essentially to have a plurality of active atoms, and the numberof an active atom on average per molecule is to be not less than 2 incalculating a plurality of predictable predominant constitutive or basicunits. For example, the number of an active hydrogen atom constituting apolymer having a repeating unit —(NH—(CH₂)₆—NH—C(═O)—(CH₂)₄—(C═O))_(n)—(polyamide 66) may be calculated based on a modeling basic unitNH₂—(CH₂)₆—NH—C(═O)—(CH₂)₄—C(═O)—OH, and when a radical-generating agentcomprises an organic peroxide, two hydrogen atoms of a terminal NH₂group comprise an active hydrogen atom (that is, S is not less than0.006). In this case, the average number N of an active hydrogen atomper polyamide 66 molecule may be calculated with the use of thefollowing formula (2) from a ratio of a terminal NH₂ group and aterminal COOH group in the polymer (polyamide 66) as an aggregate;N=2×A   (2)

wherein “A” represents the average number of a terminal NH₂ group permolecule.

For example, in a ratio of a terminal NH₂ group/terminal COOH group=1/1(molar ratio) in the resin, the number “A” of the terminal NH₂ group permolecule is 1, and the number “N” of the active hydrogen atom permolecule is equal to 2. Moreover, in 1/2 (molar ratio) of terminal NH₂group/terminal COOH group, the number “A” of the terminal NH₂ group permolecule shows 2/3, and the number “N” of the active hydrogen atom permolecule is 4/3.

Incidentally, in the case where the resin is a mixed resin comprising aplurality of resins which are different from each other in the number ofactive atoms, the number of active atoms in the mixed resin may berepresented by the average number of active atoms in each resin. Thatis, the apparent number of active atoms in the mixed resin can beestimated by calculating the number of active atoms individually basedon a basic unit for each resin constituting the mixed resin, andaveraging the calculated number of the active atom according to aproportion (weight ratio) of each resin. For example, when the mixedresin comprises (A) the above mentioned polyamide 66 (N=2) and (B) theabove mentioned polyamide 66 (N=4/3), and the molar ratio of (A)/(B) is1/1, the number “N” of the active atom per molecule of the mixed resincan be counted as 5/3. Moreover, when the mixed resin comprises (A) theabove mentioned polyamide 66 (N=2) and (C) a polyamide 66 havingcarboxyl group as all terminal groups (N=0) and the molar ratio of(A)/(C) is 3/1, the number “N” of the active atom per molecule of themixed resin can be counted as 3/2.

As the thermoplastic resin having such an active atom, there may beexemplified, among the above-mentioned resins, a polyamide-series resin,a polyester-series resin, a polyacetal-series resin, a polyphenyleneether-series resin, a polysulfide-series resin, a polyolefinic resin, apolyurethane-series resin, a thermoplastic elastomer, an amino-seriesresin and the like.

Moreover, even when a resin does not have the plural active atomsmentioned above, the resin can be utilized as a modified resin byintroducing an active atom (e.g., an amino group, an oxyalkylene group,etc.) into the resin. Such a thermoplastic resin includes, for example,a vinyl polymerization-series resin [e.g., a (meth)acrylic resin (e.g.,a poly(methyl methacrylate), a methyl methacrylate-styrene copolymer (MSresin)., a polyacrylonitrile resin, etc.); a styrenic resin (e.g., apolystyrene; a styrenic copolymer such as a AS resin and astyrene-methyl methacrylate copolymer; a styrenic grafted copolymer suchas HIPS and ABS resin), a homopolymer or copolymer comprising ahalogen-containing monomer (e.g., a polyvinyl chloride, a vinylidenechloride copolymer), a vinyl-series resin (e.g., a polyvinyl acetate, apolyvinyl alcohol)], a condensation-series resin [e.g., a polycarbonate(e.g., a bisphenol A-based polycarbonate resin), a polyimide-seriesresin, a polysulfone-series resin, a polyether sulfone-series resin, apolyether ether ketone-series resin, a polyarylate-series resin], andother resins.

In the vinyl polymerization-series resin, a modified resin may beobtained by introducing an amino group into a resin, and, for example,may be produced by copolymerization of a vinyl monomer and a monomercontaining a carboxyl group or an acid anhydride group such as(meth)acrylic acid and maleic anhydride to introduce a carboxyl group oran acid anhydride group into the vinyl polymerization-series resin, and,if necessary, reacting the resulting resin with thionyl chloride toproduce an acid chloride group, and reacting the resultant with ammonia,a mono-substituted amine (e.g., a monoalkylamine, a monoarylamine) orthe diamine mentioned above to introduce an amino group into the resin.Further, a copolymerization of a (poly)oxyalkylene glycolmono(meth)acrylate or a (poly)oxyalkylene glycolmonoalkylether(meth)acrylate with the vinyl monomer, or agraft-polymerization of the mono(meth)acrylate to the vinylpolymerization-series resin may introduce the active hydrogen atom for amodification of the vinyl polymerization-series resin.

Further, for the condensation-series resin as well as the vinylpolymerization-series resin, a modified resin may be obtained byintroducing an amino group into a resin, and a modification may becarried out by graft-polymerizing a carboxyl group- or an acid anhydridegroup-containing monomer with a resin to introduce the carboxyl group orthe acid anhydride group into the resin, if necessary, by reacting theresulting resin with thionyl chloride to produce an acid chloride group,and by reacting the acid chloride group with ammonia, a mono-substitutedamine, or the diamine mentioned above to introduce an amino group assame manner as in the above vinyl polymerization-series resin.

Moreover, the resin may comprise a resin composition comprising a resin(or a modified resin) containing a given concentration of the activeatom, and other resins. As other thermoplastic resins, there may bementioned an unmodified thermoplastic resin corresponding to themodified resin such as a styrenic resin, a (meth)acrylic resin, ahomopolymer or copolymer of a halogen-containing monomer (e.g., afluorine-containing resin), a vinyl-series resin, a polycarbonate-seriesresin, a polyimide-series resin, a polysulfone-series resin, a polyethersulfone-series resin, a polyether ether ketone-series resin, apolyarylate-series resin, a liquid-crystal polyester resin, and thelike.

In the case of an addition polymerization-series resin such as a radicalpolymerization (e.g., an unsaturated polyester, a vinylester-seriesresin, a diallyl phthalate resin, etc.) wherein the concentration of theactive atom is low, the active atom may be introduced into the resin bythe copolymerization with a monomer having the active atom. As such amonomer having the active atom, there may be mentioned, for example, amonomer having an oxyC₂₋₄alkylene unit [e.g., a (poly)oxyalkylene glycolmono(meth)acrylate such as a (poly)oxyethylene glycolmono(meth)acrylate; a (poly)oxyalkylene glycolmonoalkylether(meth)acrylate such as a (poly)oxyethylene glycolmonomethylether(meth)acrylate; a multifunctional monomer (e.g., a(poly)oxyalkylene glycol di(meth)acrylate such as a (poly)oxyethyleneglycol di(meth)acrylate, a di(meth)acrylate of a bisphenol A alkyleneoxide-adduct, etc.)], a monomer having an amide bond such as anacrylamide (an acrylamide, a methylene-bis(meth)acrylamide, a1,1-bisacrylamide-ethane, etc.).

The proportion of the resin having the active atom may be about 30 to100% by weight, preferably about 50 to 100% by weight, and morepreferably about 80 to 100% by weight, relative to the total amount ofthe resin components.

Hereinafter, resins available in the present invention will be describedin detail.

(Thermoplastic Resin)

(1) Polyamide-series Resin

The polyamide-series resin has an amide bond owing to polycondensationbetween a carboxyl group and an amino group, and includes, for example,an aliphatic polyamide-series resin, an alicyclic polyamide-seriesresin, and an aromatic polyamide-series resin. The aliphaticpolyamide-series resin is usually employed. The aliphaticpolyamide-series resin includes a condensed compound of an aliphaticdiamine component (e.g., a C₄₋₁₀alkylene diamine such astetramethylenediamine, hexamethylenediamine) and an aliphaticdicarboxylic acid component (e.g., a C₄₋₂₀alkylene dicarboxylic acidsuch as adipic acid, sebacic acid and dodecanedioic acid), for example,a polyamide 46, a polyamide 66, a polyamide 610, a polyamide 612, apolyamide 1010, a polyamide 1012, a polyamide 1212; a homopolymer or acopolymer of a lactam (e.g., a C₄₋₂₀lactam such as ε-caprolactam,ω-laurolactam) utilizing a ring-opening polymerization of the lactam, ora homopolymer or copolymer of an aminocarboxylic acid (e.g., aC₄₋₂₀aminocarboxylic acid such as ω-aminoundecanoic acid), for example,a polyamide 6, a polyamide 11, a polyamide 12; a copolyamide obtained bycopolymerizing these polyamide components (e.g., a polyamide 6/11, apolyamide 6/12, a polyamide 66/11, a polyamide 66/12) and the like.

As the alicyclic polyamide-series resin, there may be exemplified apolyamide in which an alicyclic diamine and/or an alicyclic dicarboxylicacid replaces at least part of the aliphatic diamine component and/orthe aliphatic dicarboxylic acid component. The alicyclic polyamideincludes, for example, a condensed compound of the aliphaticdicarboxylic acid component and an alicyclic diamine component [forexample, a C₅₋₈cycloalkyl diamine such as cyclohexyl diamine; abis(aminoC₅₋₈ cycloalkyl)alkane (e.g., a bis(aminocyclohexyl)alkane suchas bis(aminocyclohexyl) methane or 2,2-bis(aminocyclohexyl)propane)].

As the aromatic polyamide-series resin, there may be mentioned, apolyamide in which at least one component among the aliphatic diaminecomponents and the aliphatic dicarboxylic acid components comprises anaromatic component. The aromatic polyamide includes, for example, apolyamide in which the diamine component is substituted for an aromaticcomponent [e.g., a condensed compound of MXD-6 and an aliphaticdicarboxylic acid]; a polyamide in which the dicarboxylic acid componentcomprises an aromatic component [e.g., a condensed compound of analiphatic diamine (e.g., trimethylhexamethylenediamine) and an aromaticdicarboxylic acid (e.g., terephthalic acid, isophthalic acid)]; apolyamide in which both the diamine component and the dicarboxylic acidcomponent comprise an aromatic component [e.g., a fully aromaticpolyamide such as a poly(m-phenyleneisophthalamide (e.g., Aramid)], andothers.

The polyamide-series resin further includes a polyamide comprising adimeric acid as the dicarboxylic acid component, a polyamide having abranched structure by introducing a small amount of a polyfunctionalpolyamine and/or a polycarboxylic acid component, a modified polyamide(e.g., an N-alkoxymethylpolyamide), a high crush proof (high impact)polyamide obtained by mixing or graft-polymerizing a modifiedpolyolefin, and a polyamide elastomer having a polyether as a softsegment.

In the polyamide-series resin, an active hydrogen atom includes, forexample, a hydrogen atom of a terminal amino group, a hydrogen atombonding to an α-positioned carbon atom relative to a terminal aminogroup, a hydrogen atom bonding to a carbon atom adjacent to a group —NH—of an amide bond (e.g., a hydrogen atom of a methylene group, a hydrogenatom of a methylidyne group), in particular the hydrogen atom of theterminal amino group.

In the polyamide-series resin, the proportion of a terminal NH₂ grouprelative to a terminal COOH group is not particularly restricted, andmay be, for example, selected from the range of about 10/90 to 100/0,preferably about 20/80 to 95/5, and more preferably about 25/75 to 95/5as a molar ratio of terminal amino group/terminal carboxyl group, whenthe active hydrogen atom comprises a hydrogen atom of the terminal aminogroup and a hydrogen atom bonding to the α-positioned carbon atom.Moreover, in the case where the active hydrogen atom comprises onlyhydrogen atoms of the terminal amino group, the ratio (molar ratio) ofterminal amino group/terminal carboxyl group, maybe about 50/50 to100/0, preferably about 60/40 to 95/5, and more preferably about 70/30to 95/5.

Moreover, in the polyamide-series resin, in the case introducing anunsaturated bond as the resin (i), for example, a residual carboxylgroup or a residual amino group may be utilized as the reactive group(B), and in the case introducing the unsaturated bond as the resin (ii),the unsaturated polycarboxylic acid such as maleic acid may be utilizedas part of the copolymerizable component.

(2) Polyester-series Resin

The polyester-series resin includes, for example, an aliphaticpolyester-series resin, and an aromatic polyester-series resin. As thepolyester-series resin, an aromatic polyester-series resin (for example,a polyalkylene arylate-series resin or a saturated aromaticpolyester-series resin) is usually employed. The aromaticpolyester-series resin includes, for example, a polyC₂₋₄alkyleneterephthalate such as a polyethylene terephthalate (PET) or apolybutylene terephthalate (PBT); a polyC₂₋₄alkylene naphthalatecorresponding to the polyalkylene terephthalate (e.g., a polyethylenenaphthalate); 1,4-cyclohexyldimethylene terephthalate (PCT). Thepolyester-series resin may be a copolyester comprising an alkylenearylate unit as a predominant or main component (e.g., not less than 50%by weight). A copolymerizable component of the copolyester includes aC₂₋₆alkylene glycol such as ethylene glycol, propylene glycol,butanediol, or hexanediol; a (poly)oxyC₂₋₄alkylene glycol; anasymmetrical aromatic dicarboxylic acid such as phthalic acid orisophthalic acid, or an acid anhydride thereof; and a C₆₋₁₂aliphaticdicarboxylic acid such as adipic acid. Moreover, a branched structuremay be introduced into a linear polyester by using or modifying withsmall amounts of a polyol and/or a polycarboxylic acid.

In the case where the aromatic polyester-series resin does not have apredetermined concentration of the active atom(s), a modifiedpolyester-series resin modified with a modifying compound having theactive atom(s) (e.g., an aromatic polyester-series resin having at leastone member selected from an amino group and an oxyalkylene group) may beused. As the compound having the active atom(s), in particular, anactive hydrogen atom, there may be mentioned, for example, a polyamine[e.g., an aliphatic diamine such as a linear- orbranched-alkylenediamine having about 2 to 10 carbon atoms, e.g.,ethylenediamine, trimethylenediamine, propylenediamine,tetramethylenediamine, pentamethylenediamine, hexamethylenediamine,trimethylhexamethylenediamine, 1,7-diaminoheptane, or 1,8-diaminooctane;an alicyclic diamine such as isophorone diamine,bis(4-amino-3-methylcyclohexyl)methane, or bis(aminomethyl)cyclohexane;and an aromatic diamine such as phenylenediamine, xylylenediamine, ordiaminodiphenylmethane); and a polyol [e.g., a C₂₋₆ alkylene glycol suchas ethylene glycol, propylene glycol, butanediol, or hexanediol, a(poly)oxyC₂₋₄alkylene glycol such as a (poly)oxyethylene glycol, a(poly)oxytrimethylene glycol, a (poly)oxypropylene glycol, or a(poly)oxytetramethylene glycol]. The modification may be conducted by,for example, heating a mixture of a polyester-series resin and themodifying compound to cause an amidation, an esterification or atransesterification reaction. The degree of the modification of thepolyester-series resin may depend on an amount of the active hydrogenatom(s) in the compound, and may for example be about 0.1 to 2 mol,preferably about 0.2 to 1.5 mol, and more preferably about 0.3 to 1 molof the modifying compound relative to 1 mol of a functional group (ahydroxyl group or a carboxyl group) of the polyester-series resin. Inthe transesterification reaction, the amount of the polyol may be about1 to 50 parts by weight, and preferably about 5 to 30 parts by weightrelative to 100 parts by weight of the polyester-series resin.

In the polyester-series resin, the active hydrogen atom usuallycomprises a hydrogen atom of a methylene group of a (poly)oxyalkyleneunit. In the modified polyester-series resin, an active hydrogen atomusually comprises a hydrogen atom of a terminal amino group, a hydrogenatom bonding to an α-positioned carbon atom relative to a terminal aminogroup, a hydrogen atom bonding to a carbon atom adjacent to a group —NH—of an amide bond (e.g., a hydrogen atom of a methylene group, a hydrogenatom of a methylidyne group), and in particular the hydrogen atom of theterminal amino group.

Moreover, in the polyester-series resin, in the case introducing anunsaturated bond as the resin (i), for example, a residual carboxylgroup or a residual hydroxyl group may be utilized as the reactive group(B), and in the case introducing the unsaturated bond as the resin (ii),the unsaturated polycarboxylic acid such as maleic acid or theunsaturated polyhydric alcohol such as 2-buten-1,4-diol may be utilizedas part of the copolymerizable component.

(3) Poly(thio)ether-series Resin

The poly(thio)ether-series resin includes a polyoxyalkylene-seriesresin, a polyphenylene ether-series resin, and a polysulfide-seriesresin (polythioether-series resin). As examples of thepolyoxyalkylene-series resin, there may be mentioned apolyoxyC₂₋₄alkylene glycol such as a polyloxymethylene glycol, apolyoxyethylene glycol, a polyoxypropylene glycol, apolyoxyethylene-polyoxypropylene block-copolymer, apolyoxytetramethylene glycol, and the like. Preferred examples of thepoly(thio)ether-series resin include a polyacetal-series resin, apolyphenylene ether-series resin, a polysulfide-series resin, and apolyether ketone-series resin. Incidentally, in the case introducing anunsaturated bond as the resin (i), a residual hydroxyl group, a residualmercapto group and the like may be utilized as the reactive group (B).

(3a) Polyacetal-series Resin

The polyacetal-series resin may be a homopolymer (homopolymer offormaldehyde) comprising a regular repetition of an acetal bond, or acopolymer (e.g., a copolymer of trioxane with ethylene oxide and/or1,3-dioxolane) obtained by ring-opening polymerization or others.Moreover, the end or terminal of the polyacetal-series resin may beblocked or capped to stabilize the resin. In the polyacetal-seriesresin, an active hydrogen atom comprises, for example, a hydrogen atomof an oxymethylene unit, a hydrogen atom of an alkoxy group (inparticular methoxy group) of a blocked terminal, and in particular thehydrogen atom of the oxymethylene unit. Moreover, regarding thepolyacetal-series resin, in the case introducing an unsaturated bond asthe resin (i), a residual hydroxyl group and the like may be utilized asthe reactive group (B).

(3b) Polyphenylene ether-series Resin

The polyphenylene ether-series resin includes various resins comprising2,6-dimethylphenylene oxide as a main component, for example, acopolymer of 2,6-dimethylphenylene oxide and a phenol, and a modifiedpolyphenylene ether-series resin obtained by blending or grafting astyrenic resin in the polyphenylene-series resin. As other modifiedpolyphenylene ether-series resins, there may be mentioned apolyphenylene ether/polyamide-series, a polyphenylene ether/saturatedpolyester-series, a polyphenylene ether/polyphenylene sulfide-series, apolyphenylene ether/polyolefin-series and the like. In the case ofblending with a styrenic resin, the proportion of the styrenic resin mayfor example be about 2 to 150 parts by weight, preferably about 3 to 100parts by weight, and more preferably about 5 to 50 parts by weightrelative to 100 parts by weight of a polyphenylene ether-series resin.In the polyphenylene ether-series resin, for example, the activehydrogen atom comprises a hydrogen atom of a methyl group bonding to abenzene ring.

(3c) Polysulfide-series Resin (polythioether-series Resin)

The polysulfide-series resin is not particularly restricted to aspecific resin so far as the resin has a thio group (—S—) in the polymerchain. Such a resin includes, for example, a polyphenylene sulfideresin, a polydisulfide resin, a polybiphenylene sulfide resin, apolyketone sulfide resin, a polythioether sulfone resin, and the like.Moreover, the polysulfide-series resin may have a substituent such as anamino group, like a poly(aminophenylene sulfide). The preferredpolysulfide-series resin is a polyphenylene sulfide resin. In thepolysulfide-series resin, the active sulfur atom comprises a sulfur atomof a thio group in the main chain.

(3d) Polyether ketone-series Resin

The polyether ketone-series resin includes, for example, a polyetherketone-series resin obtained by a polycondensation between adihalogenobenzophenone (e.g., dichlorobenzophenone) and adihydrobenzophenone, a polyether-ether ketone resin obtained by apolycondensation between a dihalogenobenzophenone and a hydroquinone.

(4) Polycarbonate-series Resin

As the polycarbonate-series resin, an aliphatic polycarbonate-seriesresin may be used, and there may be usually employed an aromaticpolycarbonate-series resin [for example, an aromatic polycarbonateobtained from a reaction between an aromatic dihydroxy compound (e.g., abisphenol compound such as bisphenol A, bisphenol F, bisphenol AD orbisphenol S) and a phosgene or a diester carbonate (e.g., a diarylcarbonate such as a diphenyl carbonate, a dialkyl carbonate such as adimethyl carbonate)]. In the case introducing an unsaturated bond as theresin (i), in the polycarbonate-series resin, a residual hydroxyl groupand the like may be utilized as the reactive group (B).

(5) Polyimide-series Resin

The polyimide-series resin includes a thermoplastic polyimide-seriesresin, for example, a polyimide resin obtained by a reaction between anaromatic tetracarboxylic acid or an anhydride thereof (e.g.,benzophenone tetracarboxylic acid) and an aromatic diamine (e.g.,diaminodiphenylmethane), a polyamide imide resin, a polyester imideresin, or the like. In the case introducing an unsaturated bond as theresin (i), in the polyimide-series resin, a residual carboxyl group oracid anhydride group, a residual amino group, a residual imino group andthe like may be utilized as the reactive group (B).

(6) Polysulfone-series Resin

The polysulfone-series resin includes a polysulfone resin obtained by apolycondensation of a dihalogenodiphenyl sulfone (e.g., dichlorodiphenylsulfone) and a bisphenol (e.g., bisphenol A or a metal salt thereof), apolyether sulfone resin, a polyallyl sulfone resin (e.g., bland name“RADEL”), or the like.

(7) Polyurethane-series Resin

The polyurethane-series resin can be obtained by reacting adiisocyanate, a polyol (in particular, a diol) and, if necessary, achain-extension agent. As the diisocyanate, there are exemplified analiphatic diisocyanate such as hexamethylene diisocyanate or2,2,4-trimethylhexamethylene diisocyanate; an alicyclic diisocyanatesuch as 1,4-cyclohexane diisocyanate or isophorone diisocyanate; anaromatic diisocyanate such as phenylene diisocyanate, tolylenediisocyanate, or diphenylmethane-4,4′-diisocyanate; an araliphaticdiisocyanate such as xylylene diisocyanate; and so on. As thediisocyanate, there may be utilized a compound in which an alkyl group(e.g., methyl group) is substituted on a main chain or a ring thereof.

As the diol, there may be utilized a polyester diol (e.g., apolyesterdiol derived from a C₄₋₁₂aliphatic dicarboxylic acid componentsuch as adipic acid; a C₂₋₁₂ aliphatic diol component such as ethyleneglycol, propylene glycol, butanediol, or neopentyl glycol; a C₄₋₁₂actonecomponent such as ε-caprolactone), a polyether diol (e.g., apolyethylene glycol, a polypropylene glycol, apolyoxyethylene-polyoxypropylene block-copolymer, apolyoxytetramethylene glycol, a bisphenol A-alkylene oxide adduct), apolyester ether diol (a polyester diol in which the polyether diol isused as a part of the diol component).

Furthermore, as the chain-extension agent, a C₂₋₁₀alkylene glycol suchas ethylene glycol or propylene glycol as well as a diamine may be used.The diamine includes, for example, an aliphatic diamine such as alinear- or branched-alkylenediamine having about 2 to 10 carbon atoms(e.g., ethylenediamine, trimethylenediamine, tetramethylenediamine,pentamethylenediamine, hexamethylenediamine,trimethylhexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane)and a linear- or branched-polyalkylenepolyamine (e.g.,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,dipropylenetriamine); an alicyclic diamine such as isophoronediamine,bis(4-amino-3-methylcyclohexyl)methane, or bis(aminomethyl)cyclohexane;and an aromatic diamine such as phenylenediamine, xylylenediamine, ordiaminodiphenylmethane.

In the polyurethane-series resin, an active hydrogen atom comprises, forexample, a hydrogen atom of an alkyl group bonding to a main chain or aring of a diisocyanate (in particular a hydrogen atom at a benzylposition), a hydrogen atom in an alkylene group of a polyol or apolyoxyalkylene glycol, a hydrogen atom in an amino group of thechain-extension agent.

Moreover, in the polyurethane-series resin, in the case introducing anunsaturated bond as the resin (i), for example, a residual hydroxylgroup, a residual amino group, a residual isocyanate group and the likemay be utilized as the reactive group (B), and in the case introducingan unsaturated bond as the resin (ii), the unsaturated polycarboxylicacid such as maleic acid or the unsaturated polyhydric alcohol such as2-buten-1,4-diol may be utilized as part of the copolymerizablecomponent.

(8) Polyolefinic Resin

The polyolefinic resin includes, for example, a homopolymer or copolymerof an olefin such as a polyethylene, a polypropylene, anethylene-propylene copolymer or a poly(methylpentene-1); and a copolymerof an olefin and a copolymerizable monomer (e.g., an ethylene-vinylacetate copolymer, an ethylene-(meth)acrylic acid copolymer, anethylene-(meth)acrylate copolymer). These polyolefinic resins may beused singly or in combination.

The preferred polyolefinic resin includes a polypropylene-series resinhaving a propylene content of not less than 50% by weight (inparticular, 75 to 100% by weight), for example, a polypropylene, apropylene-ethylene copolymer, a propylene-butene copolymer, apropylene-ethylene-butene copolymer, and soon. Moreover, thepolyolefinic resin preferably has crystallinity.

In the polyolefinic resin, for example, an active hydrogen atomcomprises a hydrogen atom of a methylene group constituting a main chainof the polyolefin, a hydrogen atom of a methyl group branched from themain chain.

(9) Halogen-containing Resin

As the halogen-containing resin, there are mentioned, for example, achlorline-containing vinyl-series resin such as a polyvinyl chloride, apolyvinylidene chloride, a copolymer of vinyl chloride and vinylacetate, or a copolymer of vinylidene chloride and vinyl acetate; afluorine-containing vinyl-series resin such as a polyvinyl fluoride, apolyvinylidene fluoride, a polychlorotrifluoroethylene, or a copolymerof tetrafluoroethylene and a copolymerizable monomer. The preferredhalogen-containing resin is the fluorine-containing vinyl-series resin(e.g., the polyvinyl fluoride and the polyvinylidene fluoride).

(10) Styrenic Resin

As the styrenic resin, there are exemplified a homopolymer or copolymerof a styrenic monomer (e.g., a polystyrene, a styrene-vinyl toluenecopolymer, a styrene-α-methylstyrene copolymer), a copolymer of astyrenic monomer and a copolymerizable monomer [e.g., a styrenecopolymer such as a styrene-acrylonitrile copolymer (AS resin), a(meth)acrylate-styrene copolymer (e.g., MS resin), a styrene-maleicanhydride copolymer or a styrene-butadiene copolymer; a styrenic graftcopolymer such as a high-impact polystyrene (HIPS), anacrylonitrile-butadiene-styrene copolymer (ABS resin), anacrylonitrile-acrylic rubber-styrene copolymer (anacrylonitrile-acrylate-styrene copolymer) (AAS resin), anacrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), anacrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin),or an acrylonitrile-(ethylene-vinyl acetate copolymer)-styrene copolymer(an acrylonitrile-vinyl acetate-styrene copolymer) (AXS resin)].

(11) (Meth)acrylic Resin

The (meth)acrylic resin includes a homopolymer or copolymer of a(meth)acrylic monomer, a copolymer of a (meth)acrylic monomer and acopolymerizable monomer, and so on. The (meth)acrylic monomer mayinclude, for example, (meth)acrylic acid, a C₁₋₁₀alkyl(meth)acrylatesuch as methyl(meth)acrylate, ethyl(meth)acrylate,isopropyl(meth)acrylate, butyl(meth)acrylate, or2-ethylhexyl(meth)acrylate; a C₅₋₁₀cycloalkyl(meth)acrylate such ascyclohexyl(meth)acrylate; a C₆₋₁₀aryl(meth)acrylate such asphenyl(meth)acrylate; a hydroxyC₂₋₁₀alkyl(meth)acrylate such ashydroxyethyl(meth)acrylate; a (meth)acrylamide; a (meth)acrylonitrile;and a glycidyl(meth)acrylate. The copolymerizable monomer includes avinyl-series monomer such as vinyl acetate or vinyl chloride, a styrenicmonomer such as styrene or α-methylstyrene, and the like.

In the (meth)acrylic resin, in the case introducing an unsaturated bondas the resin (i), the reactive group (B) can be introduced by utilizinga monomer having the reactive group (B) as a copolymerizable component.

(12) Thermoplastic Elastomer

The thermoplastic elastomer includes, for example, a polyamide-serieselastomer (a copolymer comprising a polyamide as a hard segment and analiphatic polyether as a soft segment), a polyester-series elastomer (acopolymer comprising a polyalkylene arylate as a hard segment and analiphatic polyether or aliphatic polyester as a soft segment), apolyurethane-series elastomer (a copolymer comprising a polyurethanecontaining a short-chain glycol as a hard segment and an aliphaticpolyether or aliphatic polyester as a soft segment, for example, apolyester-urethane elastomer, a polyether-urethane elastomer, or thelike), a polystyrenic elastomer (a block copolymer comprising apolystyrenic block as a hard segment and a diene-polymer block or ahydrogenated block thereof as a soft segment), a polyolefinic elastomer(e.g., an elastomer comprising a polyethylene or polypropylene as a hardsegment and an ethylene-propylene rubber or an ethylene-propylene-dienerubber as a soft segment; an olefinic elastomer comprising a hardsegment and a soft segment which are different in crystallinity), apolyvinyl chloride-series elastomer, a fluorine-containing thermoplasticelastomer, and so on. As the aliphatic polyether, there may be used a(poly) oxyC₂₋₄alkylene glycol (in particular a (poly)oxyethylene glycol)exemplified in the paragraphs of the polyester-series resin and thepolyurethane-series resin. As the aliphatic polyester, for example, thepolyesterdiol mentioned in the paragraph of the polyurethane-seriesresin may be used. These thermoplastic elastomers may be used singly orin combination.

When the thermoplastic elastomer is a block copolymer, the blockstructure is not particularly restricted, and may be a triblockstructure, a multiblock structure, a star-shaped block structure orother structure.

The preferred examples of the thermoplastic elastomer include apolyamide-series elastomer, a polyester-series elastomer, apolyurethane-series elastomer, a polystyrenic elastomer, and apolyolefinic elastomer.

In the thermoplastic elastomer, an active hydrogen atom may comprise,for example, a hydrogen atom of an oxyalkylene unit constituting a softsegment.

Moreover, a vinyl polymerizable resin [e.g., a (meth)acrylic resin (apolymethyl methacrylate, a methyl methacrylate-styrene copolymer, etc.)and a styrenic resin (a polystyrene; a styrene copolymer such as ASresin; a styrene-series graft copolymer such as HIPS and ABS resin)] maybe crosslinked by copolymerization of a multifunctional polymerizablecompound having two or more functional groups (e.g., ethylene glycoldi(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycoldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.) and aconstitutive monomer.

[Rubber]

The vulcanized rubber constituting the dispersed phase is obtained byvulcanizing an unvulcanizing rubber. The rubber is not particularlylimited, and various rubbers may be used.

The rubber may include a diene-series rubber, an olefinic rubber, anacrylic rubber, a fluorine-containing rubber, a silicone-series rubber(a silicone rubber), a urethane-series rubber, an epichlorohydrin rubber(e.g., a homopolymer of epichlorohydrin (CO), a copolymer ofepichlorohydrin and ethylene oxide (E_(c) O), a copolymer furthercopolymerized with allyl glycidyl ether), a chlorosulfonatedpolyethylene, a propylene oxide rubber (GPO), an ethylene-vinyl acetatecopolymer (EAM), a polynorbornene rubber, and a modified rubber thereof(e.g., an acid-introduced (or acid-modified) rubber), and other rubbers.These rubbers may be used singly or in combination. Among these rubbers,in view of a practical use, a widely employed rubber usually includesthe diene-series rubber, the olefinic rubber, the acrylic rubber, thefluorine-containing rubber, the silicone-series rubber, theurethane-series rubber, and so on.

As the diene-series rubber, for example, there may, be mentioned anatural rubber (NR); a polymer of a diene-series monomer, such as anisoprene rubber (IR), an isobutylene-isoprene rubber (butyl rubber)(IIR), a butadiene rubber (BR), or a chloroprene rubber (CR); anacrylonitrile-diene copolymerized rubber such as anacrylonitrile-butadiene rubber (nitrile rubber) (NBR), anitrile-chloroprene rubber (NCR), a nitrile-isoprene rubber (NIR), or anacrylonitrile-isoprene-butadiene rubber (NBIR); a styrene-dienecopolymerized rubber such as a styrene-butadiene rubber (SBR, forexample, a random copolymer of styrene and butadiene, a SB-blockcopolymer comprising a styrene block and a butadiene block), astyrene-chloroprene rubber (SCR), or a styrene-isoprene rubber (SIR);and other diene-containing rubber. The diene-series rubber also includesa hydrogenated rubber, for example, a hydrogenated nitrile rubber (HNBR)or the like. Incidentally, the proportion of a styrenic component in astyrene-diene copolymerized rubber, for example, may be about 10 to 80mol %, preferably about 20 to 70 mol % and more preferably about 30 to60 mol % in terms of a monomer constituting the copolymer.

The olefinic rubber includes, for example, an ethylene-propylene rubber(EPM), an ethylene-propylene-diene rubber (EPDM), and other rubbers.

The acrylic rubber includes a rubber comprising an alkyl acrylate as amain component, such as a copolymer of an alkyl acrylate and achlorine-containing crosslinkable monomer (ACM), a copolymer of an alkylacrylate and acrylonitrile (ANM), a copolymer of an alkyl acrylate and acarboxyl group- and/or epoxy group-containing monomer, and anethylene-acrylic rubber.

As the fluorine-containing rubber, there are exemplified a rubberobtained by using a fluorine-containing monomer, for example, acopolymer of vinylidene fluoride and perfluoropropene, and if necessary,tetrafluoroethylene (FKM); a copolymer of tetrafluoroethylene andpropylene; a copolymer of tetrafluoroethylene and perfluoromethyl vinylether (FFKM).

A silicone-series rubber (Q) means an organopolysiloxane comprising aunit represented by a formula R_(a)SiO_((4-a)/2). In the formula, Rrepresents, for example, a C₁₋₁₀alkyl group such as methyl, ethyl,propyl or butyl group; a halogenated C₁₋₁₀alkyl group such as3-chloropropyl group or 3,3,3-trifluoropropyl group; a C₂₋₁₀alkenylgroup such as vinyl, allyl or butenyl group; a C₆₋₁₂aryl group such asphenyl, tolyl or naphthyl group; a C₃₋₁₀cycloalkyl group such ascyclopentyl or cyclohexyl group; a C₆₋₁₂aryl-C₁₋₄alkyl group such asbenzyl or phenethyl group. The coefficient “a” is about 1.9 to 2.1 inthe formula. The preferred R is methyl group, phenyl group, an alkenylgroup (e.g., vinyl group), and a fluoroC₁₋₆alkyl group.

A molecular structure of the silicone-series rubber is usually a linearstructure. The molecular structure may have a branched structurepartially, and may be branched. A main chain of the silicone rubber cancomprise for example, a poly(dimethylsiloxane) chain, apoly(methylvinylsiloxane) chain, a poly(methylphenyl siloxane) chain, acopolymer chain of the above mentioned siloxane unit [e.g., adimethylsiloxane-methylvinylsiloxane copolymer chain, adimethylsiloxane-methylphenylsiloxane copolymer chain, adimethylsiloxane-methyl(3,3,3-trifluoropropyl)siloxane copolymer chain,a dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymerchain]. Both terminals of the silicone rubber may for example betrimethylsilyl group, dimethylvinylsilyl group, silanol group, atriC₁₂alkoxysilyl group and the like.

The silicone-series rubber (Q) includes, for example, a methylsiliconerubber (MQ), a vinylsilicone rubber (VMQ), a phenylsilicone rubber(PMQ), a phenylvinylsilicone rubber (PVMQ), a fluorosilicone rubber(FVMQ), and the like. Further, such a silicone-series rubber includesnot only a solid rubber of the High Temperature Vulcanizable (HTV)silicone rubber but also a Room Temperature Vulcanizable (RTV) siliconerubber or Low Temperature Vulcanizable (LTV) silicone rubber, forexample a liquid or paste-like rubber.

In the case where the silicone rubber has an unsaturated bond, thenumber of the unsaturated bond of the silicone rubber constituting theunvulcanized silicone rubber may be not less than 2 (e.g., about 2 to10) per molecule on the average, preferably about 2.5 to 7, and morepreferably about 2.5 to 5 (e.g., about 2.5 to 4).

As the polyorganosiloxane in the silicone rubber or the compositionthereof, there are used a polyorganosiloxane having a double bondconcentration of about 2 to 540 mmol/kg, preferably about 3 to 300mmol/kg, and more preferably about 4 to 100 mmol/kg. Thepolyorganosiloxane may comprise a single kind of polyorganosiloxane, andmay be a mixture of plural kinds of polyorganosiloxanes (e.g., a mixtureof plural polymers different in polymerization degree).

In the case of using a plurality of polyorganosiloxanes, the double bondconcentration can be calculated from each double bond concentration ofthe plural polyorganosiloxanes constituting the mixture and acomposition ratio of the plural polyorganosiloxanes constituting themixture, etc. An average polymerization degree of the polyorganosiloxanecan be selected suitably. In the case of a polyorganosiloxane having alow polymerization degree, the average polymerization degree may forexample be about 3 to 500, and preferably about 3 to 200, and in thecase of a polyorganosiloxane having a high polymerization degree, theaverage polymerization degree may for example be about 500 to 12000, andpreferably about 1000 to 7000. When a plurality of polyorganosiloxanesdifferent in the polymerization degree are used, a proportion of apolyorganosiloxane of low polymerization degree to a polyorganosiloxaneof high polymerization degree depends on properties of a cured siliconerubber obtained by vulcanization, and the former/the latter (weightratio) is about 1/99 to 50/50, preferably about 1/99 to 10/90, and morepreferably about 2/98 to 7/93.

Further, a silicone rubber composition often comprises apolyorganohydrogensiloxane having a hydrogen atom directly bonded to asilicon atom of not less than 2 on the average per molecule. An addedamount of the polyorganohydrogensiloxane is not more than 4 parts byweight (e.g., 0.1 to 4 parts by weight), preferably not more than 3parts by weight, and more preferably not more than 2 parts by weight,relative to 100 parts by weight of the polyorganosiloxane as a maincomponent.

The urethane rubber (U) includes, for example, a polyester-basedurethane elastomer, a polyether-based urethane elastomer, and others.

As the modified rubber, there may be mentioned, for example, anacid-introduced (or acid-modified) rubber such as a carboxyl group- oracid anhydride group-containing rubber [e.g., a carboxylicstyrene-butadiene rubber (X-SBR), a carboxylic nitrile rubber (X-NBR), acarboxylic ethylene-propylene rubber (X-EP(D)M).

Incidentally, the rubber component may be used in the form ofparticulate. The form (or shape) of the rubber particulate is notparticularly limited, and may for example be an amorphous, a spherical,a elliptical, or a rod-like form (or shape). The mean particle size ofthe rubber particulate is, for example, about 0.1 to 800 μm, preferablyabout 0.5 to 500 μm, and more preferably about 0.8 to 300 μm.

The proportion of the continuous phase (or resin) relative to thedispersed phase (or unvulcanized rubber or vulcanized rubber) may besuitably set so that properties of the composite dispersion can beeffectively expressed. For example, the continuous phase/the dispersedphase (weight ratio) may be about 25/75 to 98/2, preferably about 30/70to 90/10, and more preferably about 40/60 to 80/20 (e.g., about 40/60 to65/35).

[Vulcanizing Agent]

The vulcanizing agent not only vulcanizes (or crosslinks) anunvulcanized rubber, but also activates a resin (for example, activatesa crosslinkable group of the crosslinkable resin, or activates the resinradically by a hydrogen-drawing reaction in which the active hydrogenatom is drawn from the resin) to improve adhesiveness between the resinand the rubber, and the resin phase can be bonded to the rubber phase.As the vulcanizing agent, a radical-generating agent or sulfur may beused depending on the species of the resin or the rubber. As theradical-generating agent, there may be exemplified an organic peroxide,an azo compound, a sulfur-containing organic compound, and the like.Incidentally, in the present invention, the sulfur is effective in theresin having an unsaturated bond (or bonds), the polyphenyleneether-series resin, the polysulfide-series resin, or the like in manycases. The vulcanizing agent(s) may be used singly or in combination.

The vulcanizing agent may be added to at least one component selectedfrom the unvulcanized rubber and the resin, e.g., to both components.

The organic peroxide includes, for example, a diacyl peroxide (e.g.,lauroyl peroxide, benzoyl peroxide, 4-chlorobenzoyl peroxide,2,4-dichlorobenzoyl peroxide), a dialkyl peroxide [e.g., di-t-butylperoxide, 2,5-di(t-butylperoxy)-2,5-dimethylhexane,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane,2,5-di(t-butylperoxy)-2,5-dimethylhexene-3,1,3-bis(t-butylperoxyisopropyl)benzene,dicumyl peroxide], an alkyl peroxide (e.g., t-butyl hydroperoxide,cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide,diisopropylbenzene hydroperoxide), an alkylidene peroxide [e.g.,ethylmethylketone peroxide, cyclohexanone peroxide,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane], a peracid ester(e.g., t-butyl peracetate, t-butyl perpivalate).

The azo compound includes azobisisobutylonitrile and other compounds.The sulfur-containing organic compound includes, for example, a thiuram[e.g., tetramethylthiuram monosulfide (TMTM), tetramethylthiuramdisulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabutylthiuramdisulfide (TBTD), dipentamethylenethiuram tetrasulfide (DPTT),morpholinedisulfide, an alkylphenoldisulfide].

Such a sulfur includes a powdered sulfur, a precipitated sulfur, acolloidal sulfur, an insoluble sulfur, a highly dispersant sulfur and soon. Moreover, the sulfur also includes a sulfur chloride such as sulfurmonochloride or sulfur dichloride.

As the radical-generating agent, a photopolymerization initiator alsomay be employed as far as a photoirradiation can be applied to anadhesion between the resin phase and the rubber phase. Thephotopolymerization initiator or photoinitiator may include, forexample, a benzophenone or a derivative thereof (e.g.,3,3′-dimethyl-4-methoxybenzophenone, 4,4-dimethoxybenzophenone), analkylphenylketone or a derivative thereof [e.g., acetophenone,diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-on,benzyldimethylketal, 1-hydroxycyclohexylphenylketone,2-benzyl-2-dimethylamino-1-(morpholinophenyl)-butanone], ananthraquinone or a derivative thereof (e.g., 2-methyl anthraquinone), athioxanthone or a derivative thereof (e.g., 2-chlorothioxanthone, analkylthioxanthone), a benzoin ether or a derivative thereof (e.g.,benzoin, a benzoin alkyl ether), a phosphine oxide or a derivativethereof, and others. Further, the radical-generating agent also includesa persulfate (e.g., ammonium persulfate, potassium persulfate).

Among these compounds, the preferred vulcanizing agent is the organicperoxide. The vulcanizing agent is preferably comprised in at least theunvulcanized rubber, and is usually comprised in the unvulcanized rubberin many cases.

The proportion of the vulcanizing agent can be selected within a rangeof, for example, about 0.1 to 15 parts by weight relative to 100 partsby weight of an unvulcanized rubber and/or a resin, and is usually about0.1 to 10 parts by weight, and preferably about 0.1 to 8 parts by weight(e.g., about 1 to 7 parts by weight) relative to 100 parts by weight ofan unvulcanized rubber and/or a resin.

[Vulcanization-Activating Agent]

The vulcanization-activating agent can improve wettability of the resinand the rubber to uniformly bond to each other, and depending on thevariety, the vulcanization-activating agent can crosslink the resin withthe rubber following vulcanization (or crosslinking) of an unvulcanizedrubber with a vulcanizing agent (e.g., a radical-generating agent) toimprove the crosslinking density of the resin and the rubber, therebybonding or adhering the resin to the rubber firmly. Thevulcanization-activating agent may be added to any one of the resin (orresin composition) and the unvulcanized rubber (or unvulcanized rubbercomposition), or may be added to the both components.

The vulcanization-activating agent includes a compound containing anunsaturated bond (e.g., a carbon-carbon double bond, a carbon-nitrogendouble bond, a carbon-oxygen double bond, and a carbon-sulfur doublebond) in the molecule. The unsaturated bond-containing compound may beselected depending on a vulcanizing agent to be used (e.g., aradical-generating agent), and includes an organic compound having apolymerizable unsaturated bond [for example, a vinyl-series monomer(e.g., divinylbenzene), an allyl-series monomer (e.g., diallylphthalate, triallyl phosphate, triallyl(iso)cyanurate), a (meth)acrylicmonomer], amaleimide compound, and others. The vulcanization-activatingagent(s) (or activator(s)) may be used singly or in combination.

Examples of the (meth)acrylic monomer include a bifunctional(meth)acrylate [e.g., a C₂₋₁₀alkylene glycol di(meth)acrylate such asethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate,1,4-butanediol di(meth)acrylate, hexanediol di(meth)acrylate, orneopentyl glycol di(meth)acrylate; a polyC₂₋₄alkylene glycoldi(meth)acrylate such as diethylene glycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, a polyethylene glycol di(meth)acrylate,dipropylene glycol di(meth)acrylate, tripropylene glycoldi(meth)acrylate, a polypropylene glycol di(meth)acrylate, or apolytetramethylene glycol di(meth)acrylate; glycerol di(meth)acrylate;trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate;and di(meth) acrylate of bisphenol A-C₂₋₄alkylene oxide-adduct], a tri-or poly-functional (multifunctional) (meth)acrylate [e.g., glyceroltri(meth)acrylate, trimethylolethane tri(meth)acrylate,trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate,pentaerythritol tetra(meth)acrylate, dipentaerythritoltetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate].

The maleimide-series compound includes a maleimide compound having aplurality of maleimide groups, and may be obtained by a reaction of apolyamine with a maleic anhydride. Examples of the maleimide-seriescompound include an aromatic bismaleimide [e.g.,N,N′-1,3-phenylenedimaleimide, N,N′-1,4-phenylenedimaleimide,N,N′-(3-methyl-1,4-phenylene)dimaleimide,4,4′-bis(N,N′-maleimide)diphenylmethane,4,4′-bis(N,N′-maleimide)diphenyl sulfone,4,4′-bis(N,N′-maleimide)diphenyl ether], an aliphatic bismaleimide(e.g., N,N′-1,2-ethylenebismaleimide, N,N′-1,3-propylenebismaleimide,N,N′-1,4-tetramethylenebismaleimide), etc.

The preferred vulcanization-activating agent includes a compound havinga plurality (e.g., about 2 to 6, in particular about 3 to 6) ofcarbon-carbon double bonds (polymerizable unsaturated bond) permolecule, for example, a triallyl (iso)cyanurate, a di- topolyfunctional (multifunctional) (meth)acrylate (in particular, tri- orpoly-functional (multifunctional) (meth)acrylate), and an aromaticmaleimide compound (e.g., a bismaleimide).

The amount of the vulcanization-activating agent may for example beselected from the range of about 0.1 to 10 parts by weight, preferablyabout 0.1 to 5 parts by weight, and more preferably about 0.1 to 3 partsby weight relative to 100 parts by weight of the resin and/orunvulcanized rubber.

Moreover, in the case where the unvulcanized rubber contains thevulcanizing agent and the vulcanization-activating agent, the ratio(weight ratio) of the vulcanizing agent relative to thevulcanization-activating agent [the former/the latter] may be about 2/98to70/30, preferably about10/90 to60/40 (e.g., about20/80 to 55/45), andmore preferably about 30/70 to 50/50. The use of thevulcanization-activating agent in such a ratio insures effectiveactivation of the unvulcanized rubber to the vulcanizing agent, therebyfirmly adhering the resin to the rubber in many cases.

[Polyalkenylene]

The polyalkenylene increases flowability of the rubber component (orresin component) so that the polyalkenylene can improve dispersibilityof the rubber (or resin) relative to the resin (or unvulcanized rubber)and can enhance adhesiveness between the resin phase and the rubberphase. Moreover, addition of the polyalkenylene (in particular additionto the rubber component) ensures improvement in mold-releasing propertyupon the production process of the composite dispersion,. Thepolyalkenylene may be added to any one component of the resin and theunvulcanized rubber, or added to the both components.

The polyalkenylene includes a polyC₄₋₁₅alkenylene such as apolybutadiene, a polyisoprene, a polypentenamer, a polyheptenamer, apolyoctenamer (a polyoctenylene), a poly(3-methyloctenamer), apolydecenamer, a poly(3-methyldecenamer), or a polydodecenamer, andothers. Incidentally, the polyC₄₋₁₅alkenylene may be obtained by ametathesis polymerization of a cycloolefin (for example, aC₅₋₂₀cycloolefin which may have a substituent, e.g., cyclopentene,cycloheptene, cyclooctene, cyclodecene, or cyclododecene), a partialhydrogenation of a polyalkenylene (e.g., a polybutadiene), or others.The polyalkenylene may be used singly or in combination.

The proportion of the polyalkenylene to be added may for example beabout 0.5 to 40 parts by weight, preferably about 1 to 30 parts byweight, and more preferably about 2 to 20 parts by weight relative to100 parts by weight of the resin or unvulcanized rubber.

Moreover, in the case where the unvulcanized rubber contains thevulcanizing agent and the polyalkenylene, the ratio (weight ratio) ofthe vulcanizing agent relative to the polyalkenylene [the former/thelatter] may be about 2/98 to 45/55, preferably about 2/98 to 40/60, andmore preferably about 2/98 to 35/65 (e.g., about 5/95 to 35/65). Theaddition of the vulcanizing agent and the polyalkenylene at such a ratioefficiently improves adhesiveness of the rubber to the resin in manycases.

Further, in the case where the unvulcanized rubber contains thevulcanizing agent and the resin (e.g., a polyphenylene ether resin)contains the polyalkenylene, the ratio (weight ratio) of the vulcanizingagent relative to the polyalkenylene [the former/the latter] may beabout 2/98 to 50/50, preferably about 3/97 to 40/60, and more preferablyabout 5/95 to 30/70 (e.g., about 5/95 to 20/80).

[Vulcanization Auxiliary]

In the present invention, a vulcanization auxiliary may be further used.The vulcanization auxiliary may be added to at least one component ofthe unvulcanized rubber (or unvulcanized rubber composition) and theresin (or resin composition), e.g., to the both components.

The vulcanization auxiliary may be selected depending on the species ofthe resin and the rubber, and includes, for example, an oligomer of thecondensation-series thermoplastic resin [e.g., an oligomer having anumber-average molecular weight of not more than 1000 (e.g.,about 100 to1000)], a polyamine [e.g., the polyamine described in the paragraph ofthe above-mentioned (2) polyester-series resin], a polyol [e.g., thepolyol described in the paragraph of the above-mentioned (2)polyester-series resin], a compound having a carboxyl group, acidanhydride group, or isocyanate group of not less than 1 per molecule[e.g., a mono- or polycarboxylic acid such as a dicarboxylic acid (e.g.,an aliphatic or aromatic dicarboxylic acid described in the paragraph ofthe polyamide-series resin or the polyester-series resin, an unsaturateddicarboxylic acid described in the paragraph of the above-mentionedresin (ii)), a polycarboxylic anhydride such as a dicarboxylic anhydride(an aliphatic or aromatic dicarboxylic acid such as maleic anhydride, orphthalic anhydride), a (poly)isocyanate compound such as a diisocyanate(a diisocyanate compound described in the paragraph of thepolyurethane-series resin)], a compound having a plurality of aldehydegroups, an epoxy compound, a nitrogen-containing compound (e.g., anamino resin), a compound having a methylol group or an alkoxymethylgroup, or others. The vulcanization auxiliary (or auxiliaries) may beused singly or in combination.

The preferred vulcanization auxiliary includes a compound having amolecular weight of not more than 1000 and having not less than two ofactive hydrogen atoms on the average per molecule, among active atomsrepresented by the formula (1), for example, the oligomer having anumber-average molecular weight of not more than 1000 of thecondensation-series thermoplastic resin (e.g., an oligomer of thepolyamide-series resin, an oligomer of the polyester-series resin), acompound having a carboxyl group, acid anhydride group, or isocyanategroup of not less than 1 per molecule, the above-mentioned polyamine,and others.

The amount of the vulcanization auxiliary is, for example, about 0.1 to30 parts of weight, preferably about 0.5 to 20 parts of weight, andabout 1 to 15 parts of weight, relative to 100 parts of weight of theunvulcanized rubber and/or the resin.

[Silane Coupling Agent]

In the present invention, to improve adhesiveness between the resinphase and the vulcanized rubber phase, the composite may comprise asilane coupling agent. The silane coupling agent may be added to any oneof the unvulcanized rubber (or unvulcanized rubber composition) and theresin (or resin composition), or may be added to the both components.

The silane coupling agent includes a compound having a reactive group(e.g., a hydroxyl group, an alkoxy group, a vinyl group, an amino group,an epoxy group, a mercapto group, a carboxyl group, an isocyanate group,a (meth)acryloyl group), or others.

Examples of the silane coupling agent includes

-   -   an alkoxysilane (for example, a triC₁₋₄alkoxysilane such as        trimethoxysilane or triethoxysilane, a tetraC₁₋₄alkoxysilane        such as tetramethoxysilane or tetraethoxysilane);    -   an alkoxysilane having a vinyl group (a vinyltriC₁₋₄alkoxysilane        such as vinyltrimethoxysilane or vinyltriethoxysilane);    -   an alkoxysilane having an amino group (for example, an        aminoC₂₋₄alkyltriC₁₋₄alkoxysilane such as        2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane or        3-aminopropyltriethoxysilane, an aminodiC₂₋₄        alkyldiC₁₋₄alkoxysilane such as        3-aminopropylmethyldimethoxysilane or        3-aminopropylmethylethoxysilane);    -   an alkoxysilane having an epoxy group (for example, a        glycidyloxyC₂₋₄triC₁₋₄alkoxysilane such as        3-glycidyloxypropyltrimethoxysilane, an        (epoxycycloalkyl)C₂₋₄alkyltriC₁₋₄alkoxysilane such as        2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane);    -   an alkoxysilane having a mercapto group (for example, a        mercaptoC₁₋₄alkyltriC₁₋₄alkoxysilane such as        3-mercaptopropyltrimethoxysilane, a mercaptodiC₁₋₄        alkyldiC₁₋₄alkoxysilane such as        3-mercaptopropylmethyldimethoxysilane);    -   an alkoxysilane having a carboxyl group (for example, a        carboxyC₁₋₄alkyltriC₁₋₄alkoxysilane such as        carboxymethyltrimethoxysilane, carboxymethyltriethoxysilane,        carboxyethyltrimethoxysilane, or carboxypropyltrimethoxysilane);    -   an alkoxysilane having an isocyanate group (for example, an        isocyanatoC₁₋₄alkyltriC₁₋₄alkoxysilane such as        isocyanatoethyltrimethoxysilane, isocyanatoethyltriethoxysilane,        or isocyanatopropyltrimethoxysilane);    -   an alkoxysilane having a (meth)acryloyl group (for example,        N-(3-(meth)acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,        3-(meth)acryloxypropyldimethylmethoxysilane,        3-(meth)acryloxypropyldimethylethoxysilane, or        3-(meth)acryloxypropylmethyldiethoxysilane); and others.

The amount of the silane coupling agent may be usually selected from arange so that the bonding between the resin and the rubber can beaccelerated, for example, about 1 to 10 parts by weight, preferablyabout 2 to 8 parts by weight, and more preferably about 2 to 6 parts byweight relative to 100 parts by weight of the rubber or resin.

[Other Additives]

To the above-mentioned resin (or resin composition) and/or the rubber(or rubber composition) may be added, if necessary, various additives,for example, a filler, a plasticizer or softening agent, aco-vulcanizing agent (e.g., a metal oxide such as zinc oxide), an ageresistor (e.g., a heat aging resistant, an antiozonant, an antioxidant,an ultraviolet ray absorber, a heat stabilizer), a tackifier, alubricant, a colorants (e.g., titanium oxide, carbon black), a foamingagent, a dispersant, a flame retardant, an antistatic agent, and soforth.

The filler (or reinforcer) includes, for example, a powdered orparticulate filler or reinforcer (e.g., a mica, a clay, a talc, asilicic acid, a silica, a calcium carbonate, a magnesium carbonate, acarbon black, a ferrite), a fibrous filler or reinforcer (e.g., anorganic fiber such as “Rayon”, “Nylon”, “Vinylon”, and “Aramid”; aninorganic fiber such as a carbon fiber or a glass fiber), and otherfillers.

The plasticizer is not particularly restricted so far as a plasticitycan be imparted to the resin composition or the rubber composition, andincludes a conventional plasticizer (e.g., a phthalic acid ester, analiphatic dicarboxylic acid ester, a polyester-series polymerplasticizer), and others. Moreover, in the rubber composition, aconventional softening agent (e.g., a plant oil such as linolic acid,oleic acid, castor oil, or perm oil; a mineral oil such as a paraffin, aprocess oil, or an extender) may be used.

The lubricant includes a wax (e.g., a paraffin wax, a microcrystallinewax, a polyethylene wax), a fatty acid (e.g., stearic acid), analiphatic alcohol (e.g., stearyl alcohol), a fatty acid derivative(e.g., a fatty acid ester such as butyl stearate, a fatty acid amidesuch as stearic acid amide, a metal salt of a fatty acid such as zincstearate), and others.

Examples of the foaming agent include an inorganic foaming agent such asa hydrogen carbonate (e.g., sodium hydrogen carbonate, ammonium hydrogencarbonate); an organic foaming agent such asp,p-oxybis(benzenesulfonylhydrazide), ordinitrosopentamethylenetetramine.

The content of the filler may for example be about 0 to 300 parts byweight, preferably about 0 to 200 parts by weight (e.g., about 0 to 100parts by weight), and more preferably about 0 to 50 parts by weight(e.g., about 0 to 10 parts by weight) relative to 100 parts by weight ofthe resin or the rubber. The content of the plasticizer or softeningagent may for example be about 0 to 200 parts by weight, preferablyabout 0 to 150 parts by weight, and more preferably about 0 to 120 partsby weight, relative to 100 parts by weight of the resin or the rubber.Moreover, for the co-vulcanizing agent, the age resistor, the processingauxiliary or the lubricant or the colorant, each may be used in aproportion of an effective amount, and the amount of the co-vulcanizingagent may for example be about 0 to 20 parts by weight, preferably about0.5 to 15 parts by weight, and more preferably about 1 to 10 parts byweight relative to 100 parts by weight of the resin or the rubber.

In the composite dispersion of the present invention, the resin phaseand the vulcanized rubber phase constitute the continuous phase and thedispersed phase, respectively. To such a composite can be imparted thevulcanized rubber properties (e.g., antislip property due to frictionresistance, adhesiveness to the other material, impact resistance) withthe resin properties (e.g., a mechanical property such as rigidity orstrong property, a physical property such as heat resistance) keptintact.

The composite dispersion may have an islands-in-an ocean structure inwhich a dispersed phase is independently dispersed in the continuousphase, and the shape or form of the dispersed phase may be aparticulate, an ellipsoidal, a spherical, a bar-like, a fiber-likeshape. The dispersed phase is preferably a spherical shape, and ispreferably dispersed in the continuous phase uniformly. Incidentally,the mean particle size of the dispersed phase may be, for example, about0.1 to 1000 μm, preferably about 1 to 750 μm, and more preferably about10 to 500 μm (e.g., about 50 to 150 μm), as far as properties of thedispersed phase can be expressed. Incidentally, in the case using acrosslinked or cured particle (vulcanized rubber) as a rubber, the meanparticle size of the dispersed phase corresponds to the mean particlesize of the crosslinked or cured particle.

Further, the dispersed phase particle may be bonded with the surface ofthe composite dispersion partially exposed. In such a compositedispersion, to a surface thereof can be imparted rubber properties(e.g., high flexibility and buffering property) with the properties ofthe resin constituting the continuous phase (e.g., low coefficient offriction) held.

Moreover, the obtained composite may comprise the composite dispersion,and may be a composite in which the composite dispersion and othermolded article (e.g., a resin molded article, vulcanized rubber moldedarticle) are bonded to each other at the contact surface.

In other embodiment of the present invention, as described above, acomposite dispersion comprising a specific combination of a resin and arubber insures directly firm bonding of a resin phase to a rubber phase.As concrete examples of the above specific combinations, there may bementioned the following embodiments (2a) to (2d). Incidentally, in theseembodiments, the resin may be a resin having the active atom, and theresin and/or the unvulcanized rubber may contain thevulcanization-activating agent or the polyalkenylene.

The embodiment (2a) refers to a combination of a resin, and anunvulcanized rubber containing a vulcanizing agent and avulcanization-activating agent, wherein the ratio of the vulcanizingagent relative to the vulcanization-activating agent is the same as thatdescribed for the vulcanization-activating agent [for example, thevulcanizing agent/the vulcanization-activating agent (weight ratio) isabout 2/98 to 70/30, preferably about 10/90 to 60/40 (e.g., 20/80 to55/45), and more preferably about 30/70 to 50/50).

The composite dispersion of this embodiment (2a) includes a compositedispersion in which the resin comprises a polyamide-series resin and theunvulcanized rubber comprises an unmodified rubber (e.g., a diene-seriesrubber such as NBR, SBR or HNBR, an olefinic rubber such as EPDM, afluorine-containing rubber such as FKM). That is, in the presentinvention, the resin phase and the rubber phase can be adhered to eachother by addition of the vulcanization-activating agent at theabove-mentioned ratio without utilizing a bonding reaction between anamino group and a carboxyl group.

The embodiment (2b) refers to a combination of a resin (e.g., apolyamide-series resin), and an unvulcanized rubber containing avulcanizing agent and a polyalkenylene, wherein the ratio of thevulcanizing agent relative to the polyalkenylene is the same as thatdescribed for the polyalkenylene [for example, the vulcanizing agent/thepolyalkenylene (weight ratio) is about 2/98 to 45/55, preferably about2/98 to 40/60, and more preferably about 2/98 to 35/65 (e.g., about 5/95to 35/65)].

The composite dispersion of this embodiment (2b) includes a compositedispersion in which the resin comprises a polyamide-series resin and theunvulcanized rubber comprises an unmodified rubber (e.g., a diene-seriesrubber such as NBR, SBR or HNBR, an olefinic rubber such as EPDM, afluorine-containing rubber such as FKM). In this embodiment, theflowability of the unvulcanized rubber can be improved by use of thepolyalkenylene at the above-mentioned specific ratio without utilizing abonding reaction between an amino group and a carboxyl group, wherebythe resin phase and the rubber phase can be adhered to each other.

The embodiment (2c) refers to a combination of a resin and asilicone-series unvulcanized rubber.

The composite dispersion of this embodiment (2c) includes, for example,a composite dispersion in which the resin (e.g., a polyamide-seriesresin) is directly bonded to a silicone-series rubber (for example, VMQ,PVMQ, FVMQ) which may contain a vulcanization-activating agent or apolyalkenylene. That is, use of the silicone-series rubber as a rubbercomponent ensures firm bonding of the resin phase and the rubber phaseeven in the case of using a resin not containing thevulcanization-activating agent or a crosslinkable group-containingresin, or using the unvulcanized rubber not containing thevulcanization-activating agent or the polyalkenylene at a specificratio.

The embodiment (2d) refers to a combination of a resin (e.g., apolyphenylene ether-series resin) containing a polyalkenylene, and anunvulcanized rubber containing a sulfur or a sulfur-containing organiccompound as a vulcanizing agent.

The composite dispersion of this embodiment (2d) includes a compositedispersion in which the polyphenylene ether-series resin containing apolyalkenylene and the unvulcanized rubber containing a sulfur or asulfur-containing organic compound as a vulcanizing agent are directlybonded to each other [in particular a composites dispersion in which theratio of the vulcanizing agent relative to the polyalkenylene is thesame as that described for the polyalkenylene (for example, thevulcanizing agent/the polyalkenylene is about 2/98 to 50/50, preferablyabout 3/97 to 40/60, and more preferably about 5/95 to 30/70 (e.g.,about 5/95 to 20/80))]. In such an embodiment, the continuous phase andthe dispersed phase can be bonded to each other in general-purposecombinations of the polyphenylene ether-series resin and the rubber evenin the case vulcanizing with a non-organic peroxide.

[Process for Producing Composite Dispersion]

In the present invention, a resin is kneaded with a rubber to produce acomposite dispersion in which a resin phase (continuous phase)comprising the resin is directly bonded to a rubber phase (dispersedphase) comprising a vulcanized rubber obtained by vulcanizing theunvulcanized rubber.

The rubber used in kneading the resin with the rubber may be either anunvulcanized rubber or a vulcanized rubber. In the case of using theunvulcanized rubber, vulcanization usually proceeds during the kneading.In the kneading, the vulcanizing agent may be contained in at least theunvulcanized rubber, and at least one of the resin and the vulcanizedrubber may be formed from a composition containing avulcanization-activating agent or a polyalkenylene. The vulcanizingagent and/or the vulcanization-activating agent is preferably added tothe, resin and/or the rubber beforehand, and, if necessary, may be newlyadded in the kneading process.

More specifically, the composite dispersion of the present invention canfor example be produced by melt-kneading a resin (thermoplastic resin)containing a vulcanization-activating agent or a polyalkenylene with anunvulcanized rubber (unvulcanized rubber composition) containing atleast a vulcanizing agent under heating, and cooling the resultingproduct for solidification. Both of the unvulcanized rubber and theresin show plastic property in the early state of kneading, and asvulcanization proceeds, the unvulcanized rubber becomes less plastic,the unvulcanized rubber finally turns into a vulcanized rubber, and thevulcanized rubber is dispersed in the resin phase to form a dispersedphase.

Moreover, the composite dispersion of the present invention may beobtained by kneading a resin with a vulcanized rubber. In this method,the vulcanized rubber is usually employed in the form of a vulcanizedparticulate previously produced by freeze-pulverizing or bypolymerization with a vulcanizing agent. The shape or form of theparticulate is not particularly limited as far as the shape is suitablefor the dispersed phase, and may for example be a spherical, anelliptical, or a rod-like type. Moreover, in this method, the resin (andif necessary the vulcanized rubber) may be formed from a compositioncontaining the vulcanizing agent, the vulcanization-activating agent,the polyalkenylene, and others.

The kneading may be carried out with a conventional kneading machine(e.g., an extruder, a kneader). The kneading temperature may be suitablyestablished depending on the species of the resin to be used, and forexample, the kneading temperature is about 50 to 350° C., preferablyabout 100 to 300° C., and more preferably about 150 to 250° C. (e.g.,about 170 to 230° C.).

The cooling for solidification of the melt-kneaded product may becarried out by a suitable method, for example, by water-cooling themelt-kneaded product extruded as a strand from an extruder, or others.The above-mentioned kneaded product obtained by cooling forsolidification may be processed into a pellet (and cut) by a pelletizingmachine.

The composite dispersion of the present invention may form variousshaped (or molded) articles. The composite dispersion obtained by theabove method is usually stored as a worked material (e.g., a pellet),and then is heat-melted again by a suitable processing method (e.g., ainjection molding, compression molding) to be shaped (or molded) inresponse to the purpose. The re-melting temperature of the compositedispersion depends on the species of the resin constituting thecomposite, and is, for example, about 50 to 350° C., preferably about100 to 300° C., and more preferably about 150 to 250° C. (e.g., about170 to 230° C.).

Incidentally, in the case where all the processing temperatures in thekneading process and molding process are low temperatures (e.g., below150° C.), the bonding of the resin phase with the rubber phase issometimes not enough, depending on the species of the vulcanizing agentor vulcanization-activating agent to be used, for the reason whyvulcanization of the rubber dispersed in the resin is not adequatelyproceeded, or for other reasons. Therefore, vulcanization of the rubberor crosslinking between the resin phase and the rubber phase mayculminate by setting a mold temperature in the molding process up as notless than 150° C. (e.g., 150 to 300° C.) or by heating the shapedarticle at not less than 150° C. for an adequate time with the use of aheating furnace or others.

Moreover, the shaped article formed from the composite dispersion of thepresent invention may be produced by carrying out the kneading step ofthe rubber and the resin and the molding step of the compositedispersion individually as described above, or may be produced bycombining the both steps. That is, the rubber and the resin are kneadedtogether, and then the resultant melt mixture may be directly shaped ormolded. As the shaped article obtained by such a method, there may bementioned an odd-shaped article which can be directly formed by anextruder for kneading the resin and the rubber, e.g., a film, a sheet, atube, a rod, a rail, and others.

According to the present invention, by combining a specific resin andrubber even in a wide range can be obtained a composite dispersion inwhich a continuous phase comprising a resin and a dispersed phasecomprising a vulcanized rubber are firmly bonded to each other.Moreover, the present invention ensures bonding of a resin phase to avulcanized rubber phase by a convenient process. Further, according tothe present invention, since the vulcanized rubber phase can bedispersed in the resin phase and the both phase are firmly bonded toeach other, rubber properties can be effectively imparted to the resin.

INDUSTRIAL APPLICABILITY

In thus obtained composite dispersion, the resin phase is firmly bondedto the vulcanized rubber obtained by vulcanization of the unvulcanizedrubber in the condition that the resin phase and the vulcanized rubberconstitute the continuous phase and the dispersed phase, respectively.Moreover, since the dispersed phase particle (vulcanized rubber phase)can be partially exposed to the surface of the composite dispersion,both resin and rubber properties can be expressed effectively.Therefore, the composite dispersion of the present invention can beadvantageously utilized for a variety of purposes, for example, asvarious members such as automotive parts (e.g., a vibrational absorptionbush, a spring plate, and a radiator mount), rubber cushions, valves,and electric plugs.

EXAMPLES

The following examples are intended to describe this invention infurther detail and should by no means be interpreted as defining thescope of the invention. Incidentally, in the Examples and ComparativeExamples, the following resins (or resin compositions) and rubbercompositions were used.

[Resins (A) to (F)]

Resin A1 to A6

As a thermoplastic resin, a polyamide 612 (a polycondensation product ofhexamethylenediamine and dodecanedicarboxylic acid) was produced, andthe following resins or resin compositions (A1 to A6) were prepared.Incidentally, an MOPACPM3 calculation was carried out according to thefollowing basic unit:NH₂—(CH₂)₆—NH—C(═O)—(CH₂)₁₀—C(═O)—OH

Resin (A1):

Preparation of Resin A1: An aqueous solution containing a salt ofhexamethylenediamine with dodecanedicarboxylic acid in an amount of 80%by weight was heated at 220° C. under an applied pressure (innerpressure) (17.5 kg/cm (about 1715 kPa)) in an autoclave substituted withnitrogen gas, and removed water with the nitrogen gas from the reactionsystem over 4 hours. Subsequently, the temperature of the system wasgradually increased up to 275° C. over 1 hour to remove water remainingin the system, the applied pressure (inner pressure) of the autoclavewas reduced to be an atmospheric pressure. After cooling, a polyamide612 was obtained. The resultant polymer had a number average molecularweight (Mn) of about 20000 to 25000, and a molar ratio of terminal aminogroup/terminal carboxyl group=about 1/1, and in the case where avulcanizing agent was a radical-generating agent, the number of theactive hydrogen atom having the orbital interaction energy coefficient Sof not less than 0.006 was calculated as 4 per molecule. The polymer wasused alone as Resin (A1).

Resin (A2):

Preparation of Resin A2: A vulcanization-activating agent (TRIM:trimethylolpropane trimethacrylate) (3 parts by weight) was blended to100 parts by weight of the resin (A1), and the resulting product wasused as Resin (A2).

Resin (A3):

Preparation of Resin A3: Relative to 100 parts by weight of the resin(A1), 3 parts by weight of a vulcanization-activating agent (TRIM:trimethylolpropane trimethacrylate) and 10 parts by weight of apolyoctenylene (“Vestenamer 8012” manufactured by Degussa AG) wereblended, and the resulting product was used as Resin (A3).

Resin (A4):

Preparation of Resin A4: The resin (A1) and the following resin (A6)were kneaded in a weight ratio of 1/1 [the former/the latter] by abiaxial extruder to give a polyamide 612 having a molecular weight of22000 and a molar ratio of terminal amino group/terminal carboxyl group=about 3/7. Regarding the resultant polymer, in the case where avulcanizing agent was a radical-generating agent, the number of theactive hydrogen atom having the orbital interaction energy coefficient Sof not less than 0.006 was calculated as 2.4 per molecule. The polymerwas used alone as Resin (A4).

Resin (A5):

Preparation of Resin A5: Relative to 100 parts by weight of the resin(A4), 3 parts by weight of a vulcanization-activating agent (TRIM:trimethylolpropane trimethacrylate) was blended, and the resultingproduct was used as Resin (A5).

Resin (A6):

Preparation of Resin A6: To an aqueous solution containing a salt ofhexamethylenediamine with dodecanedicarboxylic acid in an amount of 80%by weight was added a predetermined amount of dodecanedicarboxylic acid,and the mixture was heated at 220° C. under an applied pressure (innerpressure) (17.5 kg/cm² (about 1715 kPa)) in an autoclave substitutedwith nitrogen gas, and removed water with the nitrogen gas from thereaction system over 4 hours. Subsequently, the temperature of thesystem was gradually elevated up to 275° C. over 1 hour to dischargeresidual water in the system, and the applied pressure (inner pressure)of the autoclave was reduced to be an atmospheric pressure. Aftercooling, a polyamide 612 was obtained. The obtained polymer had a numberaverage molecular weight (Mn) of about 20000 and a ratio of terminalamino group/terminal carboxyl group was about 1/9, and in the case wherea vulcanizing agent was a radical-generating agent, the number of theactive hydrogen atom having the orbital interaction energy coefficient Sof not less than 0.006 was calculated as 0.8 per molecule. The polymerwas used alone as Resin (A6).

Resin (B)

A polyamide 6 was prepared as a thermoplastic resin. Avulcanization-activating agent (TRIM: trimethylolpropanetrimethacrylate) (3 parts by weight) was blended to the polyamide 6, andthe resultant product was used as Resin (B). Incidentally, an MOPACPM3calculation was carried out according to the following formula:NH₂—(CH₂)₅—C(═O)—NH—(CH₂)₅—C(═O)—OH

Preparation of polyamide 6: An aqueous solution containing E-caprolactamin an amount of 80% by weight was heated at 250 to 260° C. in thepresence of a small amount of phosphoric acid in an autoclavesubstituted with nitrogen gas to remove water with nitrogen gas from thereaction system over 4 hours. Subsequently, the temperature of theinside system was gradually elevated to 275° C. for taking 1 hour toremove a residual water to outside system. After cooling, a polyamide 6was obtained. The obtained polymer had a number average molecular weight(Mn) of about 20000 to 25000 and a ratio of terminal aminogroup/terminal carboxyl group being about 1/1, and in the case where avulcanizing agent was a radical-generating agent, the number of theactive hydrogen atom having the orbital interaction energy coefficient Sof not less than 0.006 was calculated as 4 per molecule.

Resin (C)

As a thermoplastic resin, an alicyclic polyamide [a polycondensationproduct of bis(4-aminocyclohexyl)methane and dodecanedicarboxylic acid]was prepared, and 3 parts by weight of a vulcanization-activating agent(TRIM: trimethylolpropane trimethacrylate) was mixed with the alicyclicpolyamide, and the resulting product was used as Resin (C).Incidentally, an MOPACPM3 calculation was carried out according to thefollowing basic unit:

Preparation of alicyclic polyamide: A preparation procedure wasconducted in the same manner as in the resin (A1) except that thecombination of monomers was bis(4-aminocyclohexyl)methane anddodecanedicarboxylic acid, and a polymer having a number averagemolecular weight (Mn) of 20000 to 25000 and a ratio of terminal aminogroup/terminal carboxyl group being about 1/1 was obtained. In the casewhere a vulcanizing agent was a radical-generating agent, the number ofthe active hydrogen atom having the orbital interaction energycoefficient S of the polymer of not less than 0.006 was calculated as 3per molecule.

Resins (D1 to D4)

A polybutylene terephthalate was produced as a thermoplastic resin, anda resin or resin composition was prepared. Incidentally, an MOPACPM3calculation was carried out according to the following basic unit:

Resin (D1):

Preparation of Resin D1: To a polymerization reactor (tube) which wasequipped with a stirrer, a nitrogen-introducing unit and a distillingunit and connected to a vacuum system, 1.82 g of calcium acetate and3.64 g of antimony oxide were added into the mixture of 883 g ofdistilled and purified dimethyl terephthalate and 819 g of butanediol.The tube was heated at 180° C. in an oil bath with supplying nitrogengas at a sluggish pace. At the point when a distillation amount ofmethanol was reached to a level of theory value, the mixture was stirredwith increasing the temperature of the system gradually from 250 to 260°C. and with gently enhancing a degree of vacuum to reach not higher than100 Pa. With distilling produced butanediol in small portions, thecondensation reaction was progressed for 2 to 3 hours. The relativeviscosity of the reaction product was measured ad libtum in a mixedsolvent comprising tetrachloroethane and phenol in a volume ratio (theformer/the latter) of 40/60, and the reaction was completed after thenumber average molecular weight of the product reached about 10000.Regarding the obtained polymer, in the case where a vulcanizing agentwas a radical-generating agent, the number of the active hydrogen atomhaving the orbital interaction energy coefficient S of not less than0.006 was calculated as 0 per molecule. The resultant resin was usedalone as Resin (D1).

Resin (D2):

Preparation of Resin D2: Relative to 100 parts by weight of the resin(D1), 1 part by weight of a vulcanization-activating agent (HVA2:m-phenylenebismaleimide) was blended, and the resulting product was usedas Resin (D2).

Resin (D3):

Preparation of Resin D3: Relative to 100 parts by weight of the resin(D1), 3 parts by weight of a vulcanization-activating agent (TRIM:trimethylolpropane trimethacrylate) was blended, and the obtainedproduct was used as Resin (D3).

Resin (D4):

Preparation of Resin D4: Ten (10) parts by weight of a polyoctenylene(“Vestenamer 8012” manufactured by Degussa AG) was blended relative to100 parts by weight of the resin (D1), and the obtained product was usedas Resin (D4).

Resins (E1 and E2)

As a crosslinkable resin, a polybutylene terephthalate containing anunsaturated bond was produced to prepare a resin or resin composition.

Resin (E1):

Preparation of Resin E1: A preparation procedure was conducted in thesame manner as in the resin (D) except for using 747 g of butanediol and70.4 g of butenediol in lieu of 819 g of butanediol, and a polymerhaving a number average molecular weight of about 10000 was obtained.Regarding the resultant polymer, in the case where a vulcanizing agentwas a radical-generating agent, the number of the active hydrogen atomhaving the orbital interaction energy coefficient S of not less than0.006 was calculated as 0 per molecule, and the concentration of theunsaturated bond was 4 on the average per molecule and 0.4 mol/kg. Thepolymer was used alone as Resin (El).

Resin (E2):

Preparation of Resin E2: Relative to 100 parts by weight of the resin(El), 3 parts by weight of a vulcanization-activating agent (TRIM:trimethylolpropane trimethacrylate) was blended, and the obtainedproduct was used as Resin (E2).

Resin (F)

Preparation of Resin F: Ten (10) parts by weight of a polyoctenylene(“Vestenamer 8012” manufactured by Degussa AG) was blended relative to100 parts by weight of a modified polyphenylene ether resin (“NORYL 731”manufactured by General Electric Japan), and the obtained product wasused as Resin (F). Regarding the resultant polymer, in the case where avulcanizing agent was a radical-generating agent, the number of theactive hydrogen atom was calculated as not less than 4 per molecule.Incidentally, an MOPACPM3 calculation was carried out according to thefollowing basic unit:

[Unvulcanized Rubber Composition (R)]

The following components were blended at predetermined proportions toprepare unvulcanized rubber compositions (R1 to R10).

Rubber Composition (R1)

(i) 100 parts by weight of an ethylene-propylene-diene rubber (“Keltan509×100” manufactured by DSM),

(ii) 2.5 parts by weight of a radical-generating agent [an organicperoxide (dicumyl peroxide)],

(iii) 1 part by weight of a filler (“N582” manufactured by Asahi CarbonCo., Ltd.),

(iv) 5 parts by weight of a plasticizer (“Diana Process Oil NS100”manufactured by Idemitsu Kosan Co., Ltd.),

(v) 3 parts by weight of zinc oxide, and

(vi) 1 part by weight of stearic acid

Rubber Composition (R2)

(i) 100 parts by weight of an ethylene-propylene-diene rubber (“Keltan509×100” manufactured by DSM),

(ii) 2.5 parts by weight of a radical-generating agent [an organicperoxide (dicumyl peroxide)],

(iii) 3 parts by weight of a vulcanization-activating agent (TRIM:trimethylolpropane trimethacrylate),

(iv) 1 part by weight of a filler (“N582” manufactured by Asahi CarbonCo., Ltd.), p (v) 5 parts by weight of a plasticizer (“Diana Process OilNS100” manufactured by Idemitsu Kosan Co., Ltd.),

(vi) 3 parts by weight of zinc oxide, and

(vii) 1 part by weight of stearic acid

Rubber Composition (R3)

(i) 100 parts by weight of an ethylene-propylene-diene rubber (“Keltan509×100” manufactured by DSM),

(ii)-2.5 parts by weight of a radical-generating agent [an organicperoxide (dicumyl peroxide)],

(iii) 5 parts by weight of a polyoctenylene (“Vestenamer 8012”manufactured by Degussa AG),

(iv) 1 part by weight of a filler (“N582” manufactured by Asahi CarbonCo., Ltd.),

(v) 5 parts by weight of a plasticizer (“Diana Process Oil NS100”manufactured by Idemitsu Kosan Co., Ltd.),

(vi) 3 parts by weight of zinc oxide, and

(vii) 1 part by weight of stearic acid Rubber composition (R4)

(i) 100 parts by weight of an ethylene-propylene-diene rubber (“Keltan509×100” manufactured by DSM),

(ii) 2.5 parts by weight of a radical-generating agent [an organicperoxide (dicumyl peroxide)],

(iii) 3 parts by weight of a vulcanization-activating agent (TRIM:trimethylolpropane trimethacrylate),

(iv) 5 parts by weight of a polyoctenylene (“Vestenamer 8012”manufactured by Degussa AG),

(v) 1 part by weight of a filler (“N582” manufactured by Asahi CarbonCo., Ltd.),

(vi) 5 parts by weight of a plasticizer (“Diana Process Oil NS100”manufactured by Idemitsu Kosan Co., Ltd.),

(vii) 3 parts by weight of zinc oxide, and

(viii) 1 part by weight of stearic acid

Rubber Composition (R5)

(i) 100 parts by weight of a vinyl silicone rubber (“Silicone rubberSH851” manufactured by Toray Dow Corning Co., Ltd.), and

(ii) 2.5 parts by weight of a radical-generating agent [an organicperoxide (dicumyl peroxide)]

Rubber Composition (R6)

(i) 100 parts by weight of a vinyl silicone rubber (“Silicone rubberSH851” manufactured by Toray Dow Corning Co., Ltd.),

(ii) 2.5 parts by weight of a radical-generating agent [an organicperoxide (dicumyl peroxide)], and

(iii) 0.5 part by weight of a vulcanization-activating agent (TRIM:trimethylolpropane trimethacrylate)

Rubber Composition (R7)

(i) 100 parts by weight of a fluorine-containing rubber (FKM, “Dai ELG902” manufactured by Daikin Industries Ltd.),

(ii) 2.5 parts by weight of a radical-generating agent [an organicperoxide (dicumyl peroxide)], and

(iii) 3 parts by weight of a vulcanization-activating agent (TAIC:triallylisocyanurate)

Rubber Composition (R8)

(i) 100 parts by weight of a carboxylic nitrile rubber (X-NBR) (“Nipol1072J” manufactured by Zeon Corporation),

(ii) 0.2 part by weight of a radical-generating agent [an organicperoxide (dicumyl peroxide)], and

(iii) 5 parts by weight of a polyoctenylene (“Vestenamer 8012”manufactured by Degussa AG)

Rubber Composition (R9)

(i) 100 parts by weight of a styrene-butadiene rubber [“JSR 0202”manufactured by JSR Corporation (styrene content: 46%)],

(ii) 50 parts by weight of a filler (“N582” manufactured by Asahi CarbonCo., Ltd.),

(iii) 2 parts by weight of a sulfur [powdered sulfur (Kinka-jirushi finepowdered sulfur) manufactured by Tsurumi Kagaku Kogyo K.K.],

(iv) 10 parts by weight of a plasticizer (“Diana Process Oil NS100”manufactured by Idemitsu Kosan Co., Ltd.),

(v) 5 parts by weight of zinc oxide, and

(vi) 1 part by weight of stearic acid

Rubber Composition (R10)

(i) 60 parts by weight of a styrene-butadiene rubber [“JSR 0202”manufactured by JSR Corporation (styrene content: 46%)],

(ii) 40 parts by weight of a natural rubber (made in Thailand, #3),

50 parts by weight of a filler (“N582” manufactured by Asahi Carbon Co.,Ltd.),

(iii) 2 parts by weight of a sulfur [powdered sulfur (Kinka-jirushi finepowdered sulfur) manufactured by Tsurumi Kagaku Kogyo K.K.],

(iv) 10 parts by weight of a plasticizer (“Diana Process Oil NS100”manufactured by Idemitsu Kosan Co., Ltd.),

(v) 5 parts by weight of zinc oxide, and

(vi) 1 part by weight of stearic acid

Examples 1 to 19 and Comparative Examples 1 to 5

(Preparation of Composite Dispersion)

The resin or resin composition was mixed and kneaded with a kneaderwhose temperature was regulated depending on the species of the resin.To the kneaded product was further added the above unvulcanized rubbercomposition prepared by a separate roll in the combination as shown inTable 1. Mixed and kneaded a rubber component of thereof was allowed toproceed in vulcanization to obtain a composite dispersion. The amount tobe added of the unvulcanized rubber composition was defined as 40 partsby weight relative to 60 parts by weight of the resin composition in thekneader, and the unvulcanized rubber composition was added to the resincomposition four times by 10 parts by weight over a period of 10 minutesin total. The preset temperatures of the kneader were 240° C. when theresins or resin compositions were the resins A1 to A6, B, D1 to D4, E1to E2 and F, and 270° C. when the resin or resin composition was theresin C, respectively.

(Impact Test)

The composite dispersion mentioned above was molded into a flat plate 6mm thick by compression molding, and then the plate was cut to give atest piece having a predetermined shape. The test piece was subjected toIzod impact test. For comparison, a test piece made of a polyamide 612alone, and that of a polybutylene terephthalate alone were produced tosubject to Izod impact test, respectively (Comparative Examples 1 and4).

(Drawing Test)

The composite dispersion mentioned above was molded into a flat plate 3mm thick by compression molding. Then, the flat plate was cut to a widthof 15 mm to make a test piece for a tensile test, and the test piece wassubjected to a tensile test at 50 mm/minute. The evaluation in thedrawing test was determined based on the following criteria.

“A“: The breaking elongation was not less than 200%, the disorder ordelamination phenomenon in the test piece surface was not found untilthe test piece was broken, and the whitening or fibrillation was notrecognized on the broken surface.

“B”: The breaking elongation was not less than 200%, but the whiteningor fibrillation was recognized around the broken surface.

“C”: The breaking elongation came short of 200%, and the delaminationphenomenon appeared as the test piece was drawn.

(Peel Test (or Friction Test))

The bonding strength between the rubber and the resin was measured asthe following manner.

The resin or resin composition was mixed and kneaded by a biaxialextruder to give a kneaded product, and the product was molded into aflat plate 3 mm thick by an injection molding machine. On the otherhand, the unvulcanized rubber composition was obtained by mixing eachcomponent with the use of an open roll. Then, the unvulcanized rubbercomposition was put on the upper side of the resin plate in combinationas shown in Table 1 to form a rubber layer, and the rubber layer wasvulcanized over 10 minutes by a compression molding machine regulated at170° C. with adjusting the thickness of the rubber layer to 3 mm so thatthe rubber layer was bonded to the resin plate. On this occasion,one-third of the resin plate was covered with aluminum foil to avoiddirect contact between the resin and the rubber, and the covered partwas used as a tong hold in the peel test between the rubber and theresin. Such obtained flat plate comprised of the resin-rubber compositewas cut to a vertical width of 30 mm, and the tong hold of the resinpart and that of the rubber part were fixed on a chuck of a tensiletester, respectively, to subject the flat plate to 180° peel test at atensile rate of 50 mm/minute. The evaluation of the peel test wasdetermined based on the following criteria.

“A”: Abruption proceeds by cohesive failure of the rubber layer.

“B”: Abruption proceeds by cohesive failure of the rubber layer incombination with interfacial abruption between the resin layer and therubber layer, but enough adhesion strength is recognized.

“C”: Abruption only proceeds by interfacial abruption between the resinlayer and the rubber layer, and enough adhesion strength is not found.

The results are shown in Table 1. Incidentally, in Table 1, theabbreviated expressions “VA” and “VM” mean a vulcanization-activatingagent and a polyoctenylene, respectively.

As apparent from Table 1, in each composite dispersion of Examples, thecontinuous phase and the dispersed phase were directly bonded firmly toeach other, and such a composite showed high impact strength and hightensile strength. TABLE 1 Com Ex 1 Com Ex 2 Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex6 Ex 7 Ex 8 Ex 9 Com Ex 3 Resin material Resin A1 A1 A2 A1 A1 A2 A3 A2A1 A5 A4 A6 Active atom (pcs) 4 4 4 4 4 4 4 4 4 2.4 2.4 0.8Concentration of 0 0 0 0 0 0 0 0 0 0 0 0 unsaturated bond (mol/kg) VA(parts by weight) — — 3 — — 3 3 3 — 3 — — VM (parts by weight) — — — — —— 10 — — — — — Vulcanizing agent/VM — — — — — — 14/86 — — — — — (weightratio) Rubber material Rubber — R1 R1 R2 R3 R3 R1 R5 R7 R3 R4 R1Vulcanizing agent — 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 (partsby weight) VA (parts by weight) — — — 3 — — — — 3 — 3 — Vulcanizingagent/VA — — — 45/55 — — — — 45/55 — 45/55 — (weight ratio) VM (parts byweight) — — — — 5 5 — — — 5 5 — Vulcanizing agent/VM — — — — 33/67 33/67— — — 33/67 33/67 — (weight ratio) Evaluation Peel test — B A A B A A AA A A C Impact strength 70 250 no no no no no no no no no 180 (J/m)break break break break break break break break break Drawing test — C BB B A A A A A A C comprehensive — C B B B A A A A A A C evaluation Ex 10Ex 11 Com Ex 4 Com Ex 5 Ex 12 Ex 13 Ex 14 Ex 15 Ex 16 Ex 17 Ex 18 Ex 19Resin material Resin B C D1 D1 D2 D3 D4 E1 E2 F F F Active atom (pcs) 43 0 0 0 0 0 0 0 4 or 0 0 more Concentration of 0 0 0 0 0 0 0 0.4 0.4 0 00 unsaturated bond (mol/kg) VA (parts by weight) 3 3 — — 1 3 — — 3 — — —VM (parts by weight) — — — — — — 10 — — 10 10 10 Vulcanizing agent/VM —— — — — — 15/85 — — 14/86 8/92 8/92 (weight ratio) Rubber materialRubber R8 R8 — R5 R5 R6 R5 R5 R5 R2 R9 R10 Vulcanizing agent 0.2 0.2 —2.5 2.5 2.5 2.5 2.5 2.5 2.5 2 2 (parts by weight) VA (parts by weight) —— — — — 0.5 — — — 3 — — Vulcanizing agent/VA — — — — — 83/17 — — — 45/55— — (weight ratio) VM (parts by weight) 5 5 — — — — — — — — — —Vulcanizing agent/VM 4/96 4/96 — — — — — — — — — — (weight ratio)Evaluation Peel test A A — C A A B B A A A A Impact strength no no 60220 no no no no no no no no (J/m) break break break break break breakbreak break break break Drawing test A A — C A A B A A A A Acomprehensive A A — C A A B B A A A A evaluation

1. A composite dispersion which comprises a continuous phase comprising a resin, and a dispersed phase being directly bonded to the continuous phase and comprising a vulcanized rubber formed by vulcanizing an unvulcanized rubber, wherein the resin is a resin containing a vulcanization-activating agent, or a crosslinkable group-containing resin.
 2. A composite dispersion according to claim 1, wherein the crosslinkable group-containing resin is a thermoplastic resin having an unsaturated bond, or a thermosetting resin having a crosslinkable functional group.
 3. A composite dispersion according to claim 2, wherein the thermoplastic resin having an unsaturated bond is the following resin (i) or (ii): (i) a resin produced by a reaction of a polymerizable compound having a reactive group (A) and an unsaturated bond with a thermoplastic resin having a reactive group (B) which is reactive to the reactive group (A), or (ii) a thermoplastic resin into which an unsaturated bond is introduced by copolymerization or copolycondensation.
 4. A composite dispersion according to claim 2, wherein the thermoplastic resin having an unsaturated bond has an unsaturated bond in a proportion of 0.01 to 6.6 mol relative to 1 kg of the thermoplastic resin.
 5. A composite dispersion according to claim 1, wherein the resin comprises at least one member selected from the group consisting of a polyamide-series resin, a polyester-series resin, a poly(thio)ether-series resin, a polycarbonate-series resin, a polyimide-series resin, a polysulfone-series resin, a polyurethane-series resin, a polyolefin-series resin, a halogen-containing resin, a styrenic resin, a (meth)acrylic resin, and a thermoplastic elastomer.
 6. A composite dispersion according to claim 1, wherein the resin comprises at least one member selected from the group consisting of an aliphatic polyamide-series resin, an aromatic polyester-series resin, a polyphenylene ether-series resin, and a polysulfide-series resin.
 7. A composite dispersion according to claim 1, wherein the resin has at least two atoms on the average per molecule, and each of atoms is selected from a hydrogen atom and/or a sulfur atom and has an orbital interaction energy coefficient S of not less than 0.006, wherein the orbital interaction energy coefficient S is represented by the following formula (1): S=(C _(HOMO,n))² /|E _(c) −E _(HOMO,n)|+(C _(LUMO,n))² /|E _(c) −E _(LUMO,n)|  (1) in the formula, each of E_(c), C_(HOMO,n), E_(HOMO,n), C_(LUMO,n), and E_(LUMO,n) represents a value calculated by a semiempirical molecular orbital method MOPACPM3, E_(c) representing an orbital energy (eV) of a radical of a radical-generating agent, C_(HOMO,n) representing a molecular-orbital coefficient of the highest occupied molecular orbital (HOMO) of an n-th hydrogen atom and/or sulfur atom constituting a basic unit of the resin, E_(HOMO,n) representing an orbital energy (eV) of the HOMO, C_(LUMO,n) representing a molecular-orbital coefficient of the lowest unoccupied molecular orbital (LUMO) of the n-th hydrogen atom and/or sulfur atom constituting the basic unit of the resin, and E_(LUMO,n) representing an orbital energy (eV) of the LUMO.
 8. A composite dispersion according to claim 1, wherein the vulcanized rubber comprises at least one member selected from the group consisting of a diene-series rubber, an olefinic rubber, an acrylic rubber, a fluorine-containing rubber, a silicone-series rubber, and a urethane-series rubber.
 9. A composite dispersion according to claim 1, wherein at least the unvulcanized rubber of the resin and the unvulcanized rubber comprises at least one vulcanizing agent selected from the group consisting of a radical-generating agent and a sulfur.
 10. A composite dispersion according to claim 9, wherein the radical-generating agent comprises at least one member selected from the group consisting of an organic peroxide, an azo compound, and a sulfur-containing organic compound.
 11. A composite dispersion according to claim 9, wherein the proportion of the vulcanizing agent is 0.1 to 10 parts by weight relative to 100 parts by weight of the unvulcanized rubber.
 12. A composite dispersion according to claim 1, wherein the vulcanization-activating agent comprises at least one member selected from the group consisting of an organic compound having at least two polymerizable unsaturated bonds per molecule, and a maleimide-series compound.
 13. A composite dispersion according to claim 1, wherein the proportion of the vulcanization-activating agent is 0.1 to 10 parts by weight relative to 100 parts by weight of the resin.
 14. A composite dispersion according to claim 1, wherein at least one component selected from the group consisting of the resin and the unvulcanized rubber contains a polyalkenylene.
 15. A composite dispersion according to claim 14, wherein the proportion of the polyalkenylene is 1 to 30 parts by weight relative to 100 parts by weight of the resin or the unvulcanized rubber.
 16. A composite dispersion which comprises a continuous phase comprising a resin, and a dispersed phase being directly bonded to the continuous phase and comprising a vulcanized rubber formed by vulcanizing an unvulcanized rubber, wherein a combination of the resin and/or the unvulcanized rubber is any one of the following combinations (a) to (d): (a) a combination of a resin, and an unvulcanized rubber containing a vulcanizing agent and a vulcanization-activating agent, wherein the weight ratio of the vulcanizing agent relative to the vulcanization-activating agent [the former/the latter] is 2/98 to 70/30; (b) a combination of a polyamide-series resin, and an unvulcanized rubber containing a vulcanizing agent and a polyalkenylene, wherein the weight ratio of the vulcanizing agent relative to the polyalkenylene [the former/the latter] is 2/98 to 45/55; (c) a combination of a resin and a silicone-series unvulcanized rubber; and (d) a combination of a polyphenylene ether-series resin containing a polyalkenylene, and an unvulcanized rubber containing a sulfur or a sulfur-containing organic compound as a vulcanizing agent.
 17. A composite dispersion according to claim 16, wherein the resin has at least two atoms on the average per molecule, and each of the atoms is selected from a hydrogen atom and/or a sulfur atom and has the orbital interaction energy coefficient S recited in claim 7 of not less than 0.006.
 18. A composite dispersion according to claim 16, wherein the unvulcanized rubber contains a vulcanization-activating agent.
 19. A composite dispersion according to claim 16, wherein the unvulcanized rubber contains a polyalkenylene.
 20. A composite dispersion according to claim 1 or 16, wherein the resin and/or the unvulcanized rubber has a molecular weight of not more than 1000, and comprises at least one member selected from the group consisting of the following compounds: (I) a compound having two hydrogen atoms on the average per molecule, each atom having the orbital interaction energy coefficient S recited in claim 7 of not less than 0.006; (II) a compound having not less than one group selected from the group consisting of a carboxyl group, an acid anhydride group and an isocyanate group per molecule; and (III) a silane coupling agent.
 21. A composite dispersion according to claim 1 or 16, wherein the continuous phase and the dispersed phase form an islands-in-an ocean structure.
 22. A composite dispersion according to claim 1 or 16, wherein the weight ratio of the continuous phase relative to the dispersed phase [the continuous phase/the dispersed phase] is 25/75 to 98/2.
 23. A process for producing a composite dispersion recited in claim 1 or 16, which comprises kneading a resin and an unvulcanized rubber to give the composite dispersion.
 24. A shaped article which is formed from a composite dispersion recited in claim 1 or
 16. 